Heterocyclic nitrogen-containing activators and catalyst systems for olefin polymerization

ABSTRACT

An aluminum activator and catalyst system for olefin polymerization is provided. In one aspect, the catalyst system comprises a polymerization catalyst and an activator comprising two or more heterocyclic nitrogen-containing ligands coordinated to a Group 13 atom. Preferably, the activator is a reaction product of one or more Group 13 atom-containing compounds and one or more heterocyclic nitrogen-containing compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent application Ser. No. 10/058,571, filed Jan. 28, 2002, now U.S. Pat. No. 6,841,504. This application is also a continuation-in-part of U.S. patent application Ser. No. 10/186,361, filed Jun. 28, 2002 now U.S. Pat. No. 6,703,338.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to polymerization catalyst activators, to methods of making these activators, to polymerization catalyst systems containing these activators, and to polymerization processes utilizing the same. More specifically, the present invention relates to a polymerization catalyst activator comprising two or more heterocyclic nitrogen-containing ligands coordinated to a Group 13 atom.

2. Description of the Related Art

Polymerization catalyst compounds are typically combined with an activator (or co-catalyst) to yield compositions having a vacant coordination site that will coordinate, insert, and polymerize olefins. Metallocene polymerization catalysts, for example, are typically activated with aluminoxanes which are generally oligomeric compounds containing —Al(R)—O— subunits, where R is an alkyl group. The most common aluminoxane activator is methylaluminoxane (MAO), produced by the hydrolysis of trimethylaluminum (TMA). MAO, however, is expensive to utilize because it must be added in great excess relative to the metallocene and because of the high cost of TMA. Additionally, MAO tends to be unstable as it precipitates out of solution over time.

As a result, alternative activators for metallocenes and other single-site polymerization catalysts have been discovered in recent years. For example, perfluorophenyl aluminum and borane complexes containing one anionic nitrogen-containing group have recently gained much attention.

Activator complexes having a Group 13 atom have also been suggested as a viable alternative to the expensive aluminoxane activators. For example, U.S. Pat. Nos. 6,147,173 and 6,211,105 disclose a polymerization process and polymerization catalyst where the catalyst includes an activator complex having a Group 13 element and at least one halogenated, nitrogen-containing aromatic group ligand.

Each of these alternatives, including the formation of aluminoxane, require multi-step, complicated syntheses. There is a need, therefore, to provide a simpler method of co-catalyst synthesis and catalyst activation. There is also a need to improve catalyst economics by providing a highly active co-catalyst.

SUMMARY OF THE INVENTION

An aluminum activator and catalyst system for olefin polymerization is provided. The catalyst system comprises a polymerization catalyst and an activator comprising two or more heterocyclic nitrogen-containing ligands coordinated to a Group 13 atom. In one aspect, the activator is a reaction product of one or more Group 13 atom-containing compounds and one or more heterocyclic nitrogen-containing compounds.

In another aspect, the catalyst system includes at least one activator represented by any one of the following formulas: (R′_(x)M(JY)_(y))_(n) or  (a) [((JY)_(y)R′_(x))_(n)M-O-M((R′_(x)(JY)_(y))_(n)]_(m) or  (b) (OMR′_(x)(JY)_(y))_(n)  (c) wherein:

-   -   M is a Group 13 atom;     -   O is oxygen;     -   (JY) is a heterocyclic nitrogen-containing ligand coordinated to         M;     -   R′ is a substituent group bonded to M;     -   x is an integer from 0 to 4;     -   y is 2 or more;     -   x+y=the valence of M in formula (a); x+y=the valence of M−1 in         formula (b); and x+y=valence of M−2 in formula (c);     -   n is 1 or 2 in formula (a); n is 2 in formula (b); and n is an         number from 1 to 1,000 in formula (c); and     -   m is a number from 1 to 10.

In yet another aspect, the aluminum activator includes two or more heterocyclic nitrogen-containing ligands coordinated to an aluminum atom. In one embodiment, the coordination of the heterocyclic nitrogen containing ligands to the aluminum atom causes a proton on at least one of the ligands to migrate from a first position thereof to a second position thereof. The activator is a reaction product of one or more Group 13 atom-containing compounds and one or more heterocyclic nitrogen-containing compounds selected from the group consisting of pyrroles, imidazoles, pyrazoles, pyrrolines, pyrrolidines, purines, carbazoles, indoles, phenyl indoles, 2,5, dimethyl pyrroles, 3-pentafluorophenyl pyrrole, 3,4 difluoropyrroles, derivatives thereof, radicals thereof, and combinations thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.

FIG. 1 a shows a perspective drawing of the solid-state structure for the [NC₈H₅(CH₃)][NC₈H₆(CH₃)]Al[C₂H₅]₂ molecule. Nonhydrogen atoms are represented by 50% probability thermal vibration ellipsoids and hydrogen atoms are represented by arbitrarily-small spheres which are in no way representative of their true thermal motion.

FIG. 1 b shows a perspective drawing of the solid-state structure for the [NC₈H₅(CH₃)][NC₈H₆(CH₃)]Al[C₂H₅]₂ molecule. This view is as in FIG. 1 b but atoms are now represented by: aluminum, a large cross-hatched sphere; nitrogen, medium-sized shaped spheres; carbon, medium-sized open spheres; and hydrogen, small open spheres.

FIG. 2 a shows a perspective drawing of the solid-state structure for the [NC₁₂H₈]₃Al[HNC₁₂H₈] molecule. Nonhydrogen atoms are represented by 50% probability thermal vibration ellipsoids and hydrogen atoms are represented by arbitrarily-small spheres which are in no way representative of their true thermal motion.

FIG. 2 b shows a perspective drawing of the solid-state structure for the [NC₁₂H₈]₃Al[HNC₁₂H₈] molecule. This view is as in FIG. 1 b but atoms are now represented by: aluminum, a large cross-hatched sphere; nitrogen, medium-sized shaped spheres; carbon, medium-sized open spheres; and hydrogen, small open spheres.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

An activator and a catalyst system for olefin polymerization are provided. The activator includes two or more heterocyclic ligands having four or more fused ring members, and more preferably five or more fused ring members. At least one ring of the heterocyclic ligand includes an atom selected from Group 15 or 16 of the Period Table of the Elements. As used herein, in reference to Periodic Table “Groups” of Elements, the “new” numbering scheme for the Periodic Table Groups are used as in the CRC HANDBOOK OF CHEMISTRY AND PHYSICS (David R. Lide ed., CRC Press 81^(st) ed. 2000).

Preferably, at least one ring of the heterocyclic ligand includes at least one nitrogen, oxygen, and/or sulfur atom, and more preferably includes at least one nitrogen atom. In one aspect, the two or more heterocyclic nitrogen-containing ligands include at least one indolyl and at least one indolium. In another aspect, the two or more heterocyclic nitrogen-containing ligands include at least one carbazole and at least one carbazolyl.

In a preferred embodiment, the activator is a reaction product of one or more Group 13 atom-containing compounds and one or more heterocyclic nitrogen-containing compounds. In one aspect, the one or more heterocyclic nitrogen-containing compounds is selected from the group consisting of indoles, carbazoles, pyrroles, imidazoles, purines, pyrrolines, indolines, isoquinolines, isoindolines, quinaldines, quinolines, quinoxalines, derivatives thereof, and combinations thereof. In another aspect, the one or more heterocyclic nitrogen-containing compounds is selected from the group consisting of pyrroles, imidazoles, pyrazoles, pyrrolines, pyrrolidines, purines, carbazoles, indoles, phenyl indoles, 2,5-dimethyl pyrroles, 3-pentafluorophenyl pyrroles, 3,4-difluoropyrroles, derivatives thereof, and combinations thereof. In yet another aspect, the one or more heterocyclic nitrogen-containing compounds is an indole represented by Formula (IA).

Each substituent X2 to X7 is independently selected from hydrogen, halogens, alkyl groups, aryl groups, alkoxide groups, aryloxide groups, cyano groups, nitrous groups, sulfonyl groups, nitrile groups, phosophyl groups, and alkyl substituted aryl groups wherein each group may be halogenated or partially halogenated. The one or more heterocyclic nitrogen-containing compounds may include at least one indole selected from the group consisting of 4-bromoindole, 4-fluoroindole, 5-bromoindole, 5-chloroindole, 5-fluoroindole, 4,5,6,7-tetrafluoroindole, 2-methylindole, and 3-methylindole.

In still another aspect, the one or more heterocyclic nitrogen-containing compounds is a carbazole represented by Formula (IB).

The carbazole represented by Formula (IB) may be substituted. Each substituent may be independently selected from hydrogen, halogens, alkyl groups, aryl groups, alkoxide groups, aryloxide groups, cyano groups, nitrous groups, sulfonyl groups, nitrile groups, phosophyl groups, and alkyl substituted aryl groups wherein each group may be halogenated or partially halogenated. In a particular embodiment, a substituted carbazole may include 3,6-dichlorocarbazole, 3,6-dinitrocarbazole, and 3,6-diphenylcarbazole, any derivative thereof, or any combination thereof.

In one aspect, the one or more Group 13 atom-containing compounds and the one or more heterocyclic nitrogen-containing compounds are reacted at conditions sufficient for at least one proton located at a first position on at least one of the heterocyclic nitrogen-containing compounds to migrate to a second position upon nitrogen coordination to the Group 13 atom. As a result, an activator is produced having at least one heterocyclic nitrogen-containing compound radical and at least one neutral heterocyclic nitrogen-containing compound coordinated to the Group 13 atom.

The one or more Group 13 atom-containing compounds preferably include aluminum or boron. In one aspect, the Group 13 atom-containing compounds may include aluminoxane, modified aluminoxane, tri(n-butyl) ammonium tetrakis(pentafluorophenyl)boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronapthyl boron metalloid precursor, polyhalogenated heteroborane anions, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tris(2,2′,2″-nona-fluorobiphenyl) fluoroaluminate, perchlorates, periodates, iodates and hydrates, (2,2′-bisphenyl-ditrimethylsilicate).4THF and organo-boron-aluminum compound, silylium salts and dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane)-benzimidazolide and combinations thereof.

In one aspect, the Group 13 atom-containing compound is an alkyl aluminum represented by the following formula (II): AlR₃  (II) wherein each R is independently a substituted or unsubstituted alkyl group and/or a substituted or unsubstituted aryl group. Preferably R is an alkyl group containing 1 to 30 carbon atoms. Some specific non-limiting examples of alkylaluminums include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri-iso-octylaluminum, triphenylaluminum, and combinations thereof.

In another aspect, the Group 13 atom-containing compound is an aluminoxane. Preferred aluminoxanes are oligomeric compounds containing —Al(R)—O— or —Al(R)₂—O— subunits, where R is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, triethylaluminoxane, isobutylaluminoxane, tetraethyldialuminoxane and di-isobutylaluminoxane. There are a variety of methods for preparing aluminoxane and modified aluminoxanes, such as the methods described in U.S. Pat. No. 4,542,199 and Chen and Marks, 100 Chem. Rev. 1391 (2000).

In yet another aspect, the Group 13 atom-containing compound is a boron-containing compound. Exemplary boron-containing compounds include organoboranes which include boron and one or more alkyl, aryl, or aralkyl groups. Some specific embodiments include substituted and unsubstituted trialkylboranes and triarylboranes, such as tris(pentafluorophenyl)borane, triphenylborane, tri-n-octylborane, and derivatives thereof, for example. These and other boron-containing compounds are described in U.S. Pat. Nos. 5,153,157; 5,198,401; and 5,241,025.

Preferably, the one or more Group 13 atom-containing compounds and the one or more heterocylic nitrogen-containing compounds yield an activator represented by the following Formulas (III), (IV), or (V). (R′_(x)M(JY)_(y))_(n)  (III) or [((JY)_(y)R′_(x))_(n)M-O-M((R′_(x)(JY)_(y))_(n)]_(m)  (IV) or (OMR′_(x)(JY)_(y))_(n)  (V)

In Formula (III), (IV), and (V), M is a Group 13 atom, such as boron or aluminum. (JY) represents the heterocylic nitrogen-containing ligand and is associated with M, and preferably coordinated to M. x is an integer from 0 to 4.

In Formula (III), n is 1 or 2. In Formula (IV), n is 2. In Formula (V), n is a number from 1 to 1000, preferably 1 to 100.

In Formula (IV), m is a number from 1 to 10.

In Formula (III), x+y=the valence of M.

In Formula (IV), x+y=the valence of M−1.

In Formula (V), x+y=the valence of M−2.

Each R′ is a substituent group bonded to M. Non-limiting examples of substituent R′ groups include hydrogen, linear or branched alkyl radicals, linear or branched alkenyl radicals, linear or branched alkynyl radicals, cycloalkyl radicals, aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl radicals, dialkyl radicals, carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight alkylene radicals, branched alkylene radicals, cyclic alkylene radicals, or any combination thereof.

More specific embodiments of R′ include a methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl group, including all their isomers, for example tertiary butyl, isopropyl, and the like. Other embodiments of R′ include hydrocarbyl radicals such as fluoromethyl, fluoroethyl, difluoroethyl, iodopropyl, bromohexyl, chlorobenzyl; hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; disubstitiuted boron radicals including dimethylboron for example; disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine; and Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.

Further, each R′ may include carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, or germanium atoms and the like. Still further, each R′ may include olefins such as olefinically unsaturated substituents including vinyl-terminated ligands, such as but-3-enyl, prop-2-enyl, hex-5-enyl and the like, for example. Also, at least two R′ groups, preferably two adjacent R′ groups, may be joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron, or a combination thereof. Also, a substituent group R′ such as 1-butanyl may form a carbon sigma bond to the metal M.

Catalyst Compositions

The activators described above may be utilized in conjunction with any suitable polymerization catalyst to form an active polymerization catalyst system. The catalyst system may be supported or non-supported. Typically, the mole ratio of the metal of the activator to the metal of the catalyst compound is in the range of between 0.3:1 to 10,000:1, preferably 100:1 to 5000:1, and most preferably 500:1 to 2000:1. Exemplary polymerization catalysts include metallocene catalyst compositions, Group 15-containing metal catalyst compositions, and phenoxide transition metal catalyst compositions, which are discussed in more detail below.

The term “activator” as used herein refers to any compound or component, or combination of compounds or components, capable of enhancing the ability of a catalyst to polymerize olefin monomers to form polyolefins. The term “catalyst” is used interchangeably with the term “catalyst component”, and includes any compound or component, or combination of compounds or components, that is capable of increasing the rate of a chemical reaction, such as the polymerization or oligomerization of one or more olefins. The term “catalyst system” as used herein includes at least one “catalyst” and at least one “activator”. The “catalyst system” may also include other components, such as a support for example. The catalyst system may include any number of catalysts in any combination as described herein, as well as any activator in any combination as described herein.

Metallocene Catalyst Compositions

The catalyst system may include at least one metallocene catalyst component as described herein. Metallocene catalyst compounds are generally described throughout in, for example, 1 & 2 METALLOCENE-BASED POLYOLEFINS (John Scheirs & W. Kaminsky eds., John Wiley & Sons, Ltd. 2000); G. G. Hlatky in 181 COORDINATION CHEM. REV. 243-296 (1999) and in particular, for use in the synthesis of polyethylene in 1 METALLOCENE-BASED POLYOLEFINS 261-377 (2000). The metallocene catalyst compounds as described herein include “half sandwich” and “full sandwich” compounds having one or more Cp ligands (cyclopentadienyl and ligands isolobal to cyclopentadienyl) bound to at least one Group 3 to Group 12 metal atom, and one or more leaving group(s) bound to the at least one metal atom. Hereinafter, these compounds will be referred to as “metallocenes” or “metallocene catalyst components”. The metallocene catalyst component is supported on a support material in a particular embodiment as described further below, and may be supported with or without another catalyst component.

The Cp ligands are one or more rings or ring system(s), at least a portion of which includes π-bonded systems, such as cycloalkadienyl ligands and heterocyclic analogues. The ring(s) or ring system(s) typically comprise atoms selected from the group consisting of Groups 13 to 16 atoms, and more particularly, the atoms that make up the Cp ligands are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum and combinations thereof, wherein carbon makes up at least 50% of the ring members. Even more particularly, the Cp ligand(s) are selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, non-limiting examples of which include cyclopentadienyl, indenyl, fluorenyl and other structures. Further non-limiting examples of such ligands include cyclopentadienyl, cyclopentaphenanthreneyl, indenyl, benzindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7H-dibenzofluorenyl, indeno[1,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or “H₄Ind”), substituted versions thereof (as described in more detail below), and heterocyclic versions thereof.

The metal atom “M” of the metallocene catalyst compound, as described throughout the specification and claims, may be selected from the group consisting of Groups 3 through 12 atoms and lanthanide Group atoms in one embodiment; and selected from the group consisting of Groups 3 through 10 atoms in a more particular embodiment, and selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in yet a more particular embodiment; and selected from the group consisting of Groups 4, 5 and 6 atoms in yet a more particular embodiment, and a Ti, Zr, Hf atoms in yet a more particular embodiment, and Zr in yet a more particular embodiment. The oxidation state of the metal atom “M” may range from 0 to +7 in one embodiment; and in a more particular embodiment, is +1, +2, +3, +4 or +5; and in yet a more particular embodiment is +2, +3 or +4. The groups bound the metal atom “M” are such that the compounds described below in the formulas and structures are neutral, unless otherwise indicated. The Cp ligand(s) form at least one chemical bond with the metal atom M to form the “metallocene catalyst compound”. The Cp ligands are distinct from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions.

In one aspect, the one or more metallocene catalyst components are represented by the formula (VI): Cp^(A)Cp^(B)MX_(n)  (VI) wherein M is as described above; each X is chemically bonded to M; each Cp group is chemically bonded to M; and n is 0 or an integer from 1 to 4, and either 1 or 2 in a particular embodiment.

The ligands represented by Cp^(A) and Cp^(B) in formula (VI) may be the same or different cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, either or both of which may contain heteroatoms and either or both of which may be substituted by a group R. In one embodiment, Cp^(A) and Cp^(B) are independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.

Independently, each Cp^(A) and Cp^(B) of formula (VI) may be unsubstituted or substituted with any one or combination of substituent groups R. Non-limiting examples of substituent groups R as used in structure (VI) include hydrogen radicals, alkyls, alkenyls, alkynyls, cycloalkyls, aryls, acyls, aroyls, alkoxys, aryloxys, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls, aryloxycarbonyls, carbomoyls, alkyl- and dialkyl-carbamoyls, acyloxys, acylaminos, aroylaminos, and combinations thereof.

More particular non-limiting examples of alkyl substituents R associated with formula (VI) through (V) include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, for example tertiary-butyl, isopropyl, and the like. Other possible radicals include substituted alkyls and aryls such as, for example, fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstituted boron radicals including dimethylboron for example; and disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide. Other substituents R include olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example 3-butenyl, 2-propenyl, 5-hexenyl and the like. In one embodiment, at least two R groups, two adjacent R groups in one embodiment, are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron and combinations thereof. Also, a substituent group R group such as 1-butanyl may form a bonding association to the element M.

Each X in the formula (VI) above and for the formulas/structures (II) through (V) below is independently selected from the group consisting of: any leaving group in one embodiment; halogen ions, hydrides, C₁ to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, C₁ to C₁₂ alkoxys, C₆ to C₁₆ aryloxys, C₇ to C₁₈ alkylaryloxys, C₁ to C₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, and C₁ to C₁₂ heteroatom-containing hydrocarbons and substituted derivatives thereof in a more particular embodiment; hydride, halogen ions, C₁ to C₆ alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, C₁ to C₆ alkoxys, C₆ to C₁₄ aryloxys, C₇ to C₁₆ alkylaryloxys, C₁ to C₆ alkylcarboxylates, C₁ to C₆ fluorinated alkylcarboxylates, C₆ to C₁₂ arylcarboxylates, C₇ to C₁₈ alkylarylcarboxylates, C₁ to C₆ fluoroalkyls, C₂ to C₆ fluoroalkenyls, and C₇ to C₁₈ fluoroalkylaryls in yet a more particular embodiment; hydride, chloride, fluoride, methyl, phenyl, phenoxy, benzoxy, tosyl, fluoromethyls and fluorophenyls in yet a more particular embodiment; C₁ to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, substituted C₁ to C₁₂ alkyls, substituted C₆ to C₁₂ aryls, substituted C₇ to C₂₀ alkylaryls and C₁ to C₁₂ heteroatom-containing alkyls, C₁ to C₁₂ heteroatom-containing aryls and C₁ to C₁₂ heteroatom-containing alkylaryls in yet a more particular embodiment; chloride, fluoride, C₁ to C₆ alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, halogenated C₁ to C₆ alkyls, halogenated C₂ to C₆ alkenyls, and halogenated C₇ to C₁₈ alkylaryls in yet a more particular embodiment; fluoride, methyl, ethyl, propyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, fluoromethyls (mono-, di- and trifluoromethyls) and fluorophenyls (mono-, di-, tri-, tetra- and pentafluorophenyls) in yet a more particular embodiment.

Other non-limiting examples of X groups in formula (VI) include amines, phosphines, ethers, carboxylates, dienes, hydrocarbon radicals having from 1 to 20 carbon atoms, fluorinated hydrocarbon radicals (e.g., —C₆F₅ (pentafluorophenyl)), fluorinated alkylcarboxylates (e.g., CF₃C(O)O⁻), hydrides and halogen ions and combinations thereof. Other examples of X ligands include alkyl groups such as cyclobutyl, cyclohexyl, methyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like. In one embodiment, two or more X's form a part of a fused ring or ring system.

In another aspect, the metallocene catalyst component includes those of formula (VI) where Cp^(A) and Cp^(B) are bridged to each other by at least one bridging group, (A), such that the structure is represented by formula (VII): Cp^(A)(A)Cp^(B)MX_(n)  (VII)

These bridged compounds represented by formula (VII) are known as “bridged metallocenes”. Cp^(A), Cp^(B), M, X and n in structure (VII) are as defined above for formula (VI); and wherein each Cp ligand is chemically bonded to M, and (A) is chemically bonded to each Cp. Non-limiting examples of bridging group (A) include divalent hydrocarbon groups containing at least one Group 13 to 16 atom, such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom and combinations thereof; wherein the heteroatom may also be C₁ to C₁₂ alkyl or aryl substituted to satisfy neutral valency. The bridging group (A) may also contain substituent groups R as defined above (for formula (VI)) including halogen radicals and iron. More particular non-limiting examples of bridging group (A) are represented by C₁ to C₆ alkylenes, substituted C₁ to C₆ alkylenes, oxygen, sulfur, R′₂C═, R′₂Si═, —Si(R′)₂Si(R′₂)—, R′₂Ge═, R′P═ (wherein “═” represents two chemical bonds), where R′ is independently selected from the group consisting of hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted Group 15 atoms, substituted Group 16 atoms, and halogen radical; and wherein two or more R′ may be joined to form a ring or ring system. In one embodiment, the bridged metallocene catalyst component of formula (VII) has two or more bridging groups (A).

Other non-limiting examples of bridging group (A) include methylene, ethylene, ethylidene, propylidene, isopropylidene, diphenylmethylene, 1,2-dimethylethylene, 1,2-diphenylethylene, 1,1,2,2-tetramethylethylene, dimethylsilyl, diethylsilyl, methyl-ethylsilyl, trifluoromethylbutylsilyl, bis(trifluoromethyl)silyl, di(n-butyl)silyl, di(n-propyl)silyl, di(i-propyl)silyl, di(n-hexyl)silyl, dicyclohexylsilyl, diphenylsilyl, cyclohexylphenylsilyl, t-butylcyclohexylsilyl, di(t-butylphenyl)silyl, di(p-tolyl)silyl and the corresponding moieties wherein the Si atom is replaced by a Ge or a C atom; dimethylsilyl, diethylsilyl, dimethylgermyl and diethylgermyl.

In another embodiment, bridging group (A) may also be cyclic, comprising, for example 4 to 10, 5 to 7 ring members in a more particular embodiment. The ring members may be selected from the elements mentioned above, from one or more of B, C, Si, Ge, N and O in a particular embodiment. Non-limiting examples of ring structures which may be present as or part of the bridging moiety are cyclobutylidene, cyclopentylidene, cyclohexylidene, cycloheptylidene, cyclooctylidene and the corresponding rings where one or two carbon atoms are replaced by at least one of Si, Ge, N and O, in particular, Si and Ge. The bonding arrangement between the ring and the Cp groups may be either cis-, trans-, or a combination.

The cyclic bridging groups (A) may be saturated or unsaturated and/or carry one or more substituents and/or be fused to one or more other ring structures. If present, the one or more substituents are selected from the group consisting of hydrocarbyl (e.g., alkyl such as methyl) and halogen (e.g., F, Cl) in one embodiment. The one or more Cp groups which the above cyclic bridging moieties may optionally be fused to may be saturated or unsaturated and are selected from the group consisting of those having 4 to 10, more particularly 5, 6 or 7 ring members (selected from the group consisting of C, N, O and S in a particular embodiment) such as, for example, cyclopentyl, cyclohexyl and phenyl. Moreover, these ring structures may themselves be fused such as, for example, in the case of a naphthyl group. Moreover, these (optionally fused) ring structures may carry one or more substituents. Illustrative, non-limiting examples of these substituents are hydrocarbyl (particularly alkyl) groups and halogen atoms.

The ligands Cp^(A) and Cp^(B) of formulae (VI) and (VII) are different from each other in one embodiment, and the same in another embodiment.

In yet another aspect, the metallocene catalyst components include mono-ligand metallocene compounds (e.g., mono cyclopentadienyl catalyst components) such as described in WO 93/08221 for example. In this embodiment, the at least one metallocene catalyst component is a bridged “half-sandwich” metallocene represented by the formula (VIII): Cp^(A)(A)QMX_(n)  (VIII) wherein Cp^(A) is defined above and is bound to M; (A) is a bridging group bonded to Q and Cp^(A); and wherein an atom from the Q group is bonded to M; and n is 0 or an integer from 1 to 3; 1 or 2 in a particular embodiment. In formula (VIII) above, Cp^(A), (A) and Q may form a fused ring system. The X groups and n of formula (VIII) are as defined above in formula (VI) and (VII). In one embodiment, Cp^(A) is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted versions thereof, and combinations thereof.

In formula (VIII), Q is a heteroatom-containing ligand in which the bonding atom (the atom that is bonded with the metal M) is selected from the group consisting of Group 15 atoms and Group 16 atoms in one embodiment, and selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur atom in a more particular embodiment, and nitrogen and oxygen in yet a more particular embodiment. Non-limiting examples of Q groups include alkylamines, arylamines, mercapto compounds, ethoxy compounds, carboxylates (e.g., pivalate), carbamates, azenyl, azulene, pentalene, phosphoyl, phosphinimine, pyrrolyl, pyrozolyl, carbazolyl, borabenzene other compounds comprising Group 15 and Group 16 atoms capable of bonding with M.

In yet another aspect, the at least one metallocene catalyst component is an unbridged “half sandwich” metallocene represented by the formula (IX):

 Cp^(A)MQ_(q)X_(n)  (IX)

wherein Cp^(A) is defined as for the Cp groups in (VI) and is a ligand that is bonded to M; each Q is independently bonded to M; Q is also bound to Cp^(A) in one embodiment; X is a leaving group as described above in (VI); n ranges from 0 to 3, and is 1 or 2 in one embodiment; q ranges from 0 to 3, and is 1 or 2 in one embodiment. In one embodiment, Cp^(A) is selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, substituted version thereof, and combinations thereof.

In formula (IX), Q is selected from the group consisting of ROO⁻, RO—, R(O)—, —NR—, —CR₂—, —S—, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, —H, and substituted and unsubstituted aryl groups, wherein R is selected from the group consisting of C₁ to C₆ alkyls, C₆ to C₁₂ aryls, C₁ to C₆ alkylamines, C₆ to C₁₂ alkylarylamines, C₁ to C₆ alkoxys, C₆ to C₁₂ aryloxys, and the like. Non-limiting examples of Q include C₁ to C₁₂ carbamates, C₁ to C₁₂ carboxylates (e.g., pivalate), C₂ to C₂₀ allyls, and C₂ to C₂₀ heteroallyl moieties.

Described another way, the “half sandwich” metallocenes above can be described as in formula (X), such as described in, for example, U.S. Pat. No. 6,069,213: Cp^(A)M(Q₂GZ)X_(n) or T(Cp^(A)M(Q₂GZ)X_(n))_(m)  (X)

wherein M, Cp^(A), X and n are as defined above;

Q₂GZ forms a polydentate ligand unit (e.g., pivalate), wherein at least one of the Q groups form a bond with M, and is defined such that each Q is independently selected from the group consisting of —O—, —NR—, —CR₂— and —S—; G is either carbon or silicon; and Z is selected from the group consisting of R, —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂, and hydride, providing that when Q is —NR—, then Z is selected from the group consisting of —OR, —NR₂, —SR, —SiR₃, —PR₂; and provided that neutral valency for Q is satisfied by Z; and wherein each R is independently selected from the group consisting of C₁ to C₁₀ heteroatom containing groups, C₁ to C₁₀ alkyls, C₆ to C₁₂ aryls, C₆ to C₁₂ alkylaryls, C₁ to C₁₀ alkoxys, and C₆ to C₁₂ aryloxys;

n is 1 or 2 in a particular embodiment; and

T is a bridging group selected from the group consisting of C₁ to C₁₀ alkylenes, C₆ to C₁₂ arylenes and C₁ to C₁₀ heteroatom containing groups, and C₆ to C₁₂ heterocyclic groups; wherein each T group bridges adjacent “Cp^(A)M(Q₂GZ)X_(n)” groups, and is chemically bonded to the Cp^(A) groups.

m is an integer from 1 to 7; m is an integer from 2 to 6 in a more particular embodiment.

In another aspect, the at least one metallocene catalyst component can be described more particularly in structures (XIa), (XIb), (XIc), (XId) (XIe) and (XIf):

wherein in structures (XIa) to (XIf) M is selected from the group consisting of Group 3 to Group 12 atoms, and selected from the group consisting of Group 3 to Group 10 atoms in a more particular embodiment, and selected from the group consisting of Group 3 to Group 6 atoms in yet a more particular embodiment, and selected from the group consisting of Group 4 atoms in yet a more particular embodiment, and selected from the group consisting of Zr and Hf in yet a more particular embodiment; and is Zr in yet a more particular embodiment;

wherein Q in (XIa) to (XIf) is selected from the group consisting of alkylenes, aryls, arylenes, alkoxys, aryloxys, amines, arylamines (e.g., pyridyl) alkylamines, phosphines, alkylphosphines, substituted alkyls, substituted aryls, substituted alkoxys, substituted aryloxys, substituted amines, substituted alkylamines, substituted phosphines, substituted alkylphosphines, carbamates, heteroallyls, carboxylates (non-limiting examples of suitable carbamates and carboxylates include trimethylacetate, trimethylacetate, methylacetate, p-toluate, benzoate, diethylcarbamate, and dimethylcarbamate), fluorinated alkyls, fluorinated aryls, and fluorinated alkylcarboxylates; wherein the saturated groups defining Q comprise from 1 to 20 carbon atoms in one embodiment; and wherein the aromatic groups comprise from 5 to 20 carbon atoms in one embodiment;

wherein each R* is independently: selected from the group consisting of hydrocarbylenes and heteroatom-containing hydrocarbylenes in one embodiment; and selected from the group consisting of alkylenes, substituted alkylenes and heteroatom-containing hydrocarbylenes in another embodiment; and selected from the group consisting of C₁ to C₁₂ alkylenes, C₁ to C₁₂ substituted alkylenes, and C₁ to C₁₂ heteroatom-containing hydrocarbylenes in a more particular embodiment; and selected from the group consisting of C₁ to C₄ alkylenes in yet a more particular embodiment; and wherein both R* groups are identical in another embodiment in structures (XIf);

A is as described above for (A) in structure (VII), and more particularly, selected from the group consisting of a chemical bond, —O—, —S—, —SO₂—, —NR—, ═SiR₂, ═GeR₂, ═SnR₂, —R₂SiSiR₂—, RP═, C₁ to C₁₂ alkylenes, substituted C₁ to C₁₂ alkylenes, divalent C₄ to C₁₂ cyclic hydrocarbons and substituted and unsubstituted aryl groups in one embodiment; and selected from the group consisting of C₅ to C₈ cyclic hydrocarbons, —CH₂CH₂—, ═CR₂ and ═SiR₂ in a more particular embodiment; wherein and R is selected from the group consisting of alkyls, cycloalkyls, aryls, alkoxys, fluoroalkyls and heteroatom-containing hydrocarbons in one embodiment; and R is selected from the group consisting of C₁ to C₆ alkyls, substituted phenyls, phenyl, and C₁ to C₆ alkoxys in a more particular embodiment; and R is selected from the group consisting of methoxy, methyl, phenoxy, and phenyl in yet a more particular embodiment;

wherein A may be absent in yet another embodiment, in which case each R* is defined as for R¹—R¹³;

each X is as described above in (VI);

n is an integer from 0 to 4, and from 1 to 3 in another embodiment, and 1 or 2 in yet another embodiment; and

R¹ through R¹³ are independently: selected from the group consisting of hydrogen radical, halogen radicals, C₁ to C₁₂ alkyls, C₂ to C₁₂ alkenyls, C₆ to C₁₂ aryls, C₇ to C₂₀ alkylaryls, C₁ to C₁₂ alkoxys, C₁ to C₁₂ fluoroalkyls, C₆ to C₁₂ fluoroaryls, and C₁ to C₁₂ heteroatom-containing hydrocarbons and substituted derivatives thereof in one embodiment; selected from the group consisting of hydrogen radical, fluorine radical, chlorine radical, bromine radical, C₁ to C₆ alkyls, C₂ to C₆ alkenyls, C₇ to C₁₈ alkylaryls, C₁ to C₆ fluoroalkyls, C₂ to C₆ fluoroalkenyls, C₇ to C₁₈ fluoroalkylaryls in a more particular embodiment; and hydrogen radical, fluorine radical, chlorine radical, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, hexyl, phenyl, 2,6-di-methylpheyl, and 4-tertiarybutylpheyl groups in yet a more particular embodiment; wherein adjacent R groups may form a ring, either saturated, partially saturated, or completely saturated.

The structure of the metallocene catalyst component represented by (XIa) may take on many forms such as disclosed in, for example, U.S. Pat. Nos. 5,026,798, 5,703,187, and 5,747,406, including a dimmer or oligomeric structure, such as disclosed in, for example, U.S. Pat. Nos. 5,026,798 and 6,069,213.

In a particular embodiment of the metallocene represented in (XId), R¹ and R² form a conjugated 6-membered carbon ring system that may or may not be substituted.

Non-limiting examples of metallocene catalyst components consistent with the description herein include:

cyclopentadienylzirconium X_(n),

indenylzirconium X_(n),

(1-methylindenyl)zirconium X_(n),

(2-methylindenyl)zirconium X_(n),

(1-propylindenyl)zirconium X_(n),

(2-propylindenyl)zirconium X_(n),

(1-butylindenyl)zirconium X_(n),

(2-butylindenyl)zirconium X_(n),

(methylcyclopentadienyl)zirconium X_(n),

tetrahydroindenylzirconium X_(n),

(pentamethylcyclopentadienyl)zirconium X_(n),

cyclopentadienylzirconium X_(n),

pentamethylcyclopentadienyltitanium X_(n),

tetramethylcyclopentyltitanium X_(n),

1,2,4-trimethylcyclopentadienylzirconium X_(n),

dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium X_(n),

dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2,3-trimethyl-cyclopentadienyl)zirconium X_(n),

dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(1,2-dimethyl-cyclopentadienyl)zirconium X_(n),

dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(2-methylcyclopentadienyl)zirconium X_(n),

dimethylsilyl(cyclopentadienyl)(indenyl)zirconium X_(n),

dimethylsilyl(2-methylindenyl)(fluorenyl)zirconium X_(n),

diphenylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(3-propylcyclopentadienyl)zirconium X_(n),

dimethylsilyl(1,2,3,4-tetramethylcyclopentadienyl)(3-t-butylcyclopentadienyl)zirconium X_(n),

dimethylgermyl(1,2-dimethylcyclopentadienyl)(3-isopropylcyclopentadienyl)zirconium X_(n),

dimethylsilyl(1,2,3,4-tetramethyl-cyclopentadienyl)(3-methylcyclopentadienyl) zirconium X_(n),

diphenylmethylidene(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),

diphenylmethylidene(cyclopentadienyl)(indenyl)zirconium X_(n),

iso-propylidenebis(cyclopentadienyl)zirconium X_(n),

iso-propylidene(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),

iso-propylidene(3-methylcyclopentadienyl)(9-fluorenyl)zirconium X_(n),

ethylenebis(9-fluorenyl)zirconium X_(n),

meso-ethylenebis(1-indenyl)zirconium X_(n),

ethylenebis(1-indenyl)zirconium X_(n),

ethylenebis(2-methyl-1-indenyl)zirconium X_(n),

ethylenebis(2-methyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),

ethylenebis(2-propyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),

ethylenebis(2-isopropyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),

ethylenebis(2-butyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),

ethylenebis(2-isobutyl-4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),

dimethylsilyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),

diphenyl(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),

ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium X_(n),

dimethylsilylbis(cyclopentadienyl)zirconium X_(n),

dimethylsilylbis(9-fluorenyl)zirconium X_(n),

dimethylsilylbis(1-indenyl)zirconium X_(n),

dimethylsilylbis(2-methylindenyl)zirconium X_(n),

dimethylsilylbis(2-propylindenyl)zirconium X_(n),

dimethylsilylbis(2-butylindenyl)zirconium X_(n),

diphenylsilylbis(2-methylindenyl)zirconium X_(n),

diphenylsilylbis(2-propylindenyl)zirconium X_(n),

diphenylsilylbis(2-butylindenyl)zirconium X_(n),

dimethylgermylbis(2-methylindenyl)zirconium X_(n),

dimethylsilylbis(tetrahydroindenyl)zirconium X_(n),

dimethylsilylbis(tetramethylcyclopentadienyl)zirconium X_(n),

dimethylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),

diphenylsilyl(cyclopentadienyl)(9-fluorenyl)zirconium X_(n),

diphenylsilylbis(indenyl)zirconium X_(n),

cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium X_(n),

cyclotetramethylenesilyl(tetramethylcyclopentadienyl)(cyclopentadienyl) zirconium X_(n),

cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2-methylindenyl)zirconium X_(n),

cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(3-methylcyclopentadienyl)zirconium X_(n),

cyclotrimethylenesilylbis(2-methylindenyl)zirconium X_(n),

cyclotrimethylenesilyl(tetramethylcyclopentadienyl)(2,3,5-trimethylcyclopentadienyl)zirconium X_(n),

cyclotrimethylenesilylbis(tetramethylcyclopentadienyl)zirconium X_(n),

dimethylsilyl(tetramethylcyclopentadieneyl)(N-tert-butylamido)titanium X_(n),

bis(cyclopentadienyl)chromium X_(n),

bis(cyclopentadienyl)zirconium X_(n),

bis(n-butylcyclopentadienyl)zirconium X_(n),

bis(n-dodecyclcyclopentadienyl)zirconium X_(n),

bis(ethylcyclopentadienyl)zirconium X_(n),

bis(iso-butylcyclopentadienyl)zirconium X_(n),

bis(iso-propylcyclopentadienyl)zirconium X_(n),

bis(methylcyclopentadienyl)zirconium X_(n),

bis(n-oxtylcyclopentadienyl)zirconium X_(n),

bis(n-pentylcyclopentadienyl)zirconium X_(n),

bis(n-propylcyclopentadienyl)zirconium X_(n),

bis(trimethylsilylcyclopentadienyl)zirconium X_(n),

bis(1,3-bis(trimethylsilyl)cyclopentadienyl)zirconium X_(n),

bis(1-ethyl-2-methylcyclopentadienyl)zirconium X_(n),

bis(1-ethyl-3-methylcyclopentadienyl)zirconium X_(n),

bis(pentamethylcyclopentadienyl)zirconium X_(n),

bis(pentamethylcyclopentadienyl)zirconium X_(n),

bis(1-propyl-3-methylcyclopentadienyl)zirconium X_(n),

bis(1-n-butyl-3-methylcyclopentadienyl)zirconium X_(n),

bis(1-isobutyl-3-methylcyclopentadienyl)zirconium X_(n),

bis(1-propyl-3-butylcyclopentadienyl)zirconium X_(n),

bis(1,3-n-butylcyclopentadienyl)zirconium X_(n),

bis(4,7-dimethylindenyl)zirconium X_(n),

bis(indenyl)zirconium X_(n),

bis(2-methylindenyl)zirconium X_(n),

cyclopentadienylindenylzirconium X_(n),

bis(n-propylcyclopentadienyl)hafnium X_(n),

bis(n-butylcyclopentadienyl)hafnium X_(n),

bis(n-pentylcyclopentadienyl)hafnium X_(n),

(n-propyl cyclopentadienyl)(n-butyl cyclopentadienyl)hafnium X_(n),

bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium X_(n),

bis(trimethylsilyl cyclopentadienyl)hafnium X_(n),

bis(2-n-propylindenyl)hafnium X_(n),

bis(2-n-butylindenyl)hafnium X_(n),

dimethylsilylbis(n-propylcyclopentadienyl)hafnium X_(n),

dimethylsilylbis(n-butylcyclopentadienyl)hafnium X_(n),

bis(9-n-propylfluorenyl)hafnium X_(n),

bis(9-n-butylfluorenyl)hafnium X_(n),

(9-n-propylfluorenyl)(2-n-propylindenyl)hafnium X_(n),

bis(1-n-propyl-2-methylcyclopentadienyl)hafnium X_(n),

(n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium X_(n),

dimethylsilyl(tetramethyleyclopentadienyl)(cyclobutylamido)titanium X_(n),

dimethylsilyl(tetramethyleyclopentadienyl)(cyclopentylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titanium X_(n),

dimethylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(cyclobutylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(cyclopentylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium, X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(n-octylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(n-decylamido)titanium X_(n),

methylphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(cyclopropylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(cyclobutylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(cyclopentylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(cyclohexylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(cycloheptylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(cyclooctylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(cyclononylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(cyclodecylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(cycloundecylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(sec-butylamido)titanium X_(n),

diphenylsilyl(tetramethyleyclopentadienyl)(n-octylamido)titanium X_(n),

diphenylsilyl(tetramethyleyclopentadienyl)(n-decylamido)titanium X_(n),

diphenylsilyl(tetramethylcyclopentadienyl)(n-octadecylamido)titanium X_(n),

and derivatives thereof.

By “derivatives thereof”, it is meant any substitution or ring formation as described above in one embodiment; and in particular, replacement of the metal “M” (Cr, Zr, Ti or Hf) with an atom selected from the group consisting of Cr, Zr, Hf and Ti; and replacement of the “X” group with any of C₁ to C₅ alkyls, C₆ aryls, C₆ to C₁₀ alkylaryls, fluorine or chlorine; n is 1, 2 or 3.

It is contemplated that the metallocene catalysts components described above include their structural or optical or enantiomeric isomers (racemic mixture), and may be a pure enantiomer in one embodiment.

As used herein, a single, bridged, asymmetrically substituted metallocene catalyst component having a racemic and/or meso isomer does not, itself, constitute at least two different bridged, metallocene catalyst components.

The “metallocene catalyst component” may comprise any combination of any “embodiment” described herein.

Group 15-Containing Catalyst Compositions

“Group 15-containing catalyst components”, as referred to herein, include Group 3 to Group 12 metal complexes, wherein the metal is 2 to 4 coordinate, the coordinating moiety or moieties including at least two Group 15 atoms, and up to four Group 15 atoms. In one embodiment, the Group 15-containing catalyst component is a complex of a Group 4 metal and from one to four ligands such that the Group 4 metal is at least 2 coordinate, the coordinating moiety or moieties including at least two nitrogens. Representative Group 15-containing compounds are disclosed in, for example, WO 98/46651, WO 99/01460; EP A1 0 893,454; EP A1 0 894 005; U.S. Pat. Nos. 5,318,935; 5,889,128 6,333,389 B2 and 6,271,325 B1.

In one embodiment, the Group 15-containing catalyst components may include Group 4 imino-phenol complexes, Group 4 bis(amide) complexes, and Group 4 pyridyl-amide complexes that are active towards olefin polymerization to any extent.

The Group 15-containing catalyst component may be more particularly described by the following formula (XII): α_(a)β_(b)γ_(g)MX_(n)  (XII) wherein β and γ are groups that each comprise at least one Group 14 to Group 16 atom; and β (when present) and γ are groups bonded to M through between 2 and 6 Group 14 to Group 16 atoms, at least two atoms being Group 15-containing atoms.

More particularly, β and γ are groups selected from Group 14 and Group 15-containing: alkyls, aryls, alkylaryls, and heterocyclic hydrocarbons, and chemically bonded combinations thereof in one embodiment; and selected from Group 14 and Group 15-containing: C₁ to C₁₀ alkyls, C₆ to C₁₂ aryls, C₆ to C₁₈ alkylaryls, and C₄ to C₁₂ heterocyclic hydrocarbons, and chemically bonded combinations thereof in a more particular embodiment; and selected from C₁ to C₁₀ alkylamines, C₁ to C₁₀ alkoxys, C₆ to C₂₀ alkylarylamines, C₆ to C₁₈ alkylaryloxys, and C₄ to C₁₂ nitrogen containing heterocyclic hydrocarbons, and C₄ to C₁₂ alkyl substituted nitrogen containing heterocyclic hydrocarbons and chemically bonded combinations thereof in yet a more particular embodiment; and selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls, C₁ to C₆ alkyl substituted groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls; C₁ to C₆ alkylamine substituted groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls, amine substituted anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, and indolyls; hydroxy substituted groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, and indolyls; methyl-substituted phenylamines, and chemically bonded combinations thereof in yet a more particular embodiment;

α is a linking (or “bridging”) moiety that, when present, forms a chemical bond to each of β and γ, or two γ's, thus forming a “γαγ” or “γαβ” ligand bound to M; α may also comprise a Group 14 to Group 16 atom which may be bonded to M through the Group 14 to Group 16 atom in one embodiment; and more particularly, α is a divalent bridging group selected from alkylenes, arylenes, alkenylenes, heterocyclic arylenes, alkylarylenes, heteroatom containing alkylenes, heteroatom containing alkenylenes and heterocyclic hydrocarbonylenes in one embodiment; and selected from C₁ to C₁₀ alkylenes, C₂ to C₁₀ alkenylenes, C₆ to C₁₂ arylenes, C₁ to C₁₀ divalent ethers, C₆ to C₁₂ O— or N-containing arylenes, C₂ to C₁₀ alkyleneamines, C₆ to C₁₂ aryleneamines, and substituted derivatives thereof in yet a more particular embodiment;

a is an integer from 0 to 2; a is either 0 or 1 in a more particular embodiment; and a is 1 in yet a more particular embodiment; b is an integer from 0 to 2; g is an integer from 1 to 2; wherein in one embodiment, a is 1, b is 0 and g is 2; M is selected from Group 3 to Group 12 atoms in one embodiment; and selected from Group 3 to Group 10 atoms in a more particular embodiment; and selected from Group 3 to Group 6 atoms in yet a more particular embodiment; and selected from Ni, Cr, Ti, Zr and Hf in yet a more particular embodiment; and selected from Zr and Hf in yet a more particular embodiment; each X is as defined above; and n is an integer from 0 to 4 in one embodiment; and an integer from 1 to 3 in a more particular embodiment; and an integer from 2 to 3 in yet a more particular embodiment.

As used herein, “chemically bonded combinations thereof” means that adjacent groups, (β and γ groups) may form a chemical bond between them; in one embodiment, the β and γ groups are chemically bonded through one or more α groups there between.

As used herein, the terms “alkyleneamines”, “aryleneamines”, describe alkylamines and arylamines (respectively) that are deficient by two hydrogens, thus forming chemical bonds with two adjacent γ groups, or adjacent β and γ groups. Thus, an example of an alkyleneamine is —CH₂CH₂N(CH₃)CH₂CH₂—, and an example of a heterocyclic hydrocarbylene or aryleneamine is —C₅H₃N— (divalent pyridine). An “alkylene-arylamine” is a group such as, for example, —CH₂CH₂(C₅H₃N)CH₂CH₂—.

Described another way, the Group 15-containing catalyst component is represented by the structures (XIII) and (XIV):

wherein E and Z are Group 15 elements independently selected from nitrogen and phosphorus in one embodiment; and nitrogen in a more particular embodiment;

L is selected from Group 15 atoms, Group 16 atoms, Group 15-containing hydrocarbylenes and a Group 16 containing hydrocarbylenes in one embodiment; wherein R³ is absent when L is a Group 16 atom; in yet a more particular embodiment, when R³ is absent, L is selected from heterocyclic hydrocarbylenes; and in yet a more particular embodiment, L is selected from nitrogen, phosphorous, anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls; C₁ to C₆ alkyl substituted groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, and indolyls; C₁ to C₆ alkylamine substituted groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, indolyls; amine substituted anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, and indolyls; hydroxy substituted groups selected from anilinyls, pyridyls, quinolyls, pyrrolyls, pyrimidyls, purinyls, imidazyls, and indolyls; methyl-substituted phenylamines, substituted derivatives thereof, and chemically bonded combinations thereof;

L′ is selected from Group 15 atoms, Group 16 atoms, and Group 14 atoms in one embodiment; and selected from Group 15 and Group 16 atoms in a more particular embodiment; and is selected from groups as defined by L above in yet a more particular embodiment, wherein “EZL” and “EZL” may be referred to as a “ligand”, the EZL and EZL′ ligands comprising the R* and R¹—R⁷ groups;

wherein L and L′ may or may not form a bond with M;

y is an integer ranging from 0 to 2 (when y is 0, group L′, *R and R³ are absent);

M is selected from Group 3 to Group 5 atoms, Group 4 atoms in a more particular embodiment, and selected from Zr and Hf in yet a more particular embodiment;

n is an integer ranging from 1 to 4 in one embodiment; n is an integer ranging from 2 to 3 in a more particular embodiment;

each X is as defined above;

R¹ and R² are independently: divalent bridging groups selected from alkylenes, arylenes, heteroatom containing alkylenes, heteroatom containing arylenes, substituted alkylenes, substituted arylenes and substituted heteroatom containing alkylenes, wherein the heteroatom is selected from silicon, oxygen, nitrogen, germanium, phosphorous, boron and sulfur in one embodiment; selected from C₁ to C₂₀ alkylenes, C₆ to C₁₂ arylenes, heteroatom-containing C₁ to C₂₀ alkylenes and heteroatom-containing C₆ to C₁₂ arylenes in a more particular embodiment; and in yet a more particular embodiment selected from —CH₂—, —C(CH₃)₂—, —C(C₆H₅)₂—, —CH₂CH₂—, —CH₂CH₂CH₂—, —Si(CH₃)₂—, —Si(C₆H₅)₂—, —C₆H₁₀—, —C₆H₄—, and substituted derivatives thereof, the substitutions including C₁ to C₄ alkyls, phenyl, and halogen radicals;

R³ is absent in one embodiment; a group selected from hydrocarbyl groups, hydrogen radical, halogen radicals, and heteroatom-containing groups in a more particular embodiment; and selected from linear alkyls, cyclic alkyls, and branched alkyls having 1 to 20 carbon atoms in yet a more particular embodiment;

*R is absent in one embodiment; a group selected from hydrogen radical, Group 14 atom containing groups, halogen radicals, and a heteroatom-containing groups in yet a more particular embodiment;

R⁴ and R⁵ are independently: groups selected from alkyls, aryls, substituted aryls, cyclic alkyls, substituted cyclic alkyls, cyclic arylalkyls, substituted cyclic arylalkyls and multiple ring systems in one embodiment, each group having up to 20 carbon atoms, and between 3 and 10 carbon atoms in a more particular embodiment; selected from C₁ to C₂₀ alkyls, C₁ to C₂₀ aryls, C₁ to C₂₀ arylalkyls, and heteroatom-containing groups (for example PR₃, where R is an alkyl group) in yet a more particular embodiment; and

R⁶ and R⁷ are independently: absent in one embodiment; groups selected from hydrogen radicals, halogen radicals, heteroatom-containing groups and hydrocarbyls in a more particular embodiment; selected from linear, cyclic and branched alkyls having from 1 to 20 carbon atoms in yet a more particular embodiment;

wherein R¹ and R² may be associated with one another, and/or R⁴ and R⁵ may be associated with one another as through a chemical bond.

Described yet more particularly, the Group 15-containing catalyst component can be described as the embodiments shown in structures (IV), (V) and (VI) (where “N” is nitrogen):

wherein structure (XV) represents pyridyl-amide structures, structure (XVI) represents imino-phenol structures, and structure (XVII) represents bis(amide) structures; wherein w is an integer from 1 to 3, and 1 or 2 in a more particular embodiment, and 1 in yet a more particular embodiment; M is a Group 3 to Group 13 element, a Group 3 to Group 6 element in a more particular embodiment, and a Group 4 element in yet a more particular embodiment; each X is independently selected from hydrogen radicals, halogen ions (desirably, anions of fluorine, chlorine, and bromine); C₁ to C₆ alkyls; C₁ to C₆ fluoroalkyls, C₆ to C₁₂ aryls; C₆ to C₁₂ fluoroalkyls, C₁ to C₆ alkoxys, C₆ to C₁₂ aryloxys, and C₇ to C₁₈ alkylaryloxys; n is an integer ranging from 0 to 4, and from 1 to 3 in a more particular embodiment, and from 2 to 3 in yet a more particular embodiment, and 2 in yet a more particular embodiment;

and further, wherein in structures (XV), (XVI) and (XVII), R¹′ is selected from hydrocarbylenes and heteroatom-containing hydrocarbylenes in one embodiment, and selected from —SiR₂—, alkylenes, arylenes, alkenylenes and substituted alkylenes, substituted alkenylenes and substituted arylenes in another embodiment; and selected from —SiR₂—, C₁ to C₆ alkylenes, C₆ to C₁₂ arylenes, C₁ to C₆ substituted alkylenes and C₆ to C₁₂ substituted arylenes in another embodiment, wherein R is selected from C₁ to C₆ alkyls and C₆ to C₁₂ aryls; and

R²′, R³′, R⁴′, R⁵′, R⁶′ and R* are independently selected from hydride, C₁ to C₁₀ alkyls, C₆ to C₁₂ aryls, C₆ to C₁₈ alkylaryls, C₄ to C₁₂ heterocyclic hydrocarbyls, substituted C₁ to C₁₀ alkyls, substituted C₆ to C₁₂ aryls, substituted C₆ to C₁₈ alkylaryls, and substituted C₄ to C₁₂ heterocyclic hydrocarbyls and chemically bonded combinations thereof in one embodiment; wherein R* is absent in a particular embodiment; and in another embodiment, R*—N represents a nitrogen containing group or ring such as a pyridyl group or a substituted pyridyl group that is bridged by the R¹′ groups. In yet another embodiment, R*—N is absent, and the R¹′ groups form a chemical bond to one another.

In one embodiment of structures (XV), (XVI) and (XVII), R¹′ is selected from methylene, ethylene, 1-propylene, 2-propylene, ═Si(CH₃)₂, ═Si(phenyl)₂, —CH═, —C(CH₃)═, —C(phenyl)₂—, —C(phenyl)═ (wherein “═” represents two chemical bonds), and the like.

In a particular embodiment of structure (XVI), R²′ and R⁴′ are selected from 2-methylphenyl, 2-n-propylphenyl, 2-iso-propylphenyl, 2-iso-butylphenyl, 2-tert-butylphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methyl-4-chlorophenyl, 2-n-propyl-4-chlorophenyl, 2-iso-propyl-4-chlorophenyl, 2-iso-butyl-4-chlorophenyl, 2-tert-butyl-4-chlorophenyl, 2-methyl-4-fluorophenyl, 2-n-propyl-4-fluorophenyl, 2-iso-propyl-4-fluorophenyl, 2-iso-butyl-4-fluorophenyl, 2-tert-butyl-4-fluorophenyl, 2-methyl-4-bromophenyl, 2-n-propyl-4-bromophenyl, 2-iso-propyl-4-bromophenyl, 2-iso-butyl-4-bromophenyl, 2-tert-butyl-4-bromophenyl, and the like.

In yet another particular embodiment of structures (XV) and (XVII), R²′ and R³′ are selected from 2-methylphenyl, 2-n-propylphenyl, 2-iso-propylphenyl, 2-iso-butylphenyl, 2-tert-butylphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 4-methylphenyl, 4-n-propylphenyl, 4-iso-propylphenyl, 4-iso-butylphenyl, 4-tert-butylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 6-methylphenyl, 6-n-propylphenyl, 6-iso-propylphenyl, 6-iso-butylphenyl, 6-tert-butylphenyl, 6-fluorophenyl, 6-chlorophenyl, 6-bromophenyl, 2,6-dimethylphenyl, 2,6-di-n-propylphenyl, 2,6-di-iso-propylphenyl, 2,6-di-isobutylphenyl, 2,6-di-tert-butylphenyl, 2,6-difluorophenyl, 2,6-dichlorophenyl, 2,6-dibromophenyl, 2,4,6-trimethylphenyl, 2,4,6-tri-n-propylphenyl, 2,4,6-tri-iso-propylphenyl, 2,4,6-tri-iso-butylphenyl, 2,4,6-tri-tert-butylphenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, 2,3,4,5,6-pentafluorophenyl, 2,3,4,5,6-pentachlorophenyl, 2,3,4,5,6-pentabromophenyl, and the like.

In another embodiment of structures (XV), (XVI) and (XVII), X is independently selected from fluoride, chloride, bromide, methyl, ethyl, phenyl, benzyl, phenyloxy, benzloxy, 2-phenyl-2-propoxy, 1-phenyl-2-propoxy, 1-phenyl-2-butoxy, 2-phenyl-2-butoxy and the like.

As used herein, “chemically bonded combinations” means that adjacent groups may form a chemical bond between them, thus forming a ring system, either saturated, partially unsaturated, or aromatic.

Non-limiting examples of the Group 15-containing catalyst component are represented by the structures (XVIIIa)-(XVIIIf) (where “N” is nitrogen):

wherein in structures (XVIIIa) through (XVIIIf) M is selected from Group 4 atoms in one embodiment; and M is selected from Zr and Hf in a more particular embodiment;, and wherein R¹ through R¹¹ in structures (XVIIIa) through (XVIIIf) are selected from hydride, fluorine radical, chlorine radical, bromine radical, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and phenyl; and X is selected from fluorine ion, chlorine ion, bromine ion, methyl, phenyl, benzyl, phenyloxy and benzyloxy; and n is an integer ranging from 0 to 4, and from 2 to 3 in a more particular embodiment.

The Group 15-containing catalyst components are prepared by methods known in the art, such as those disclosed in, for example, EP 0 893 454 A1, U.S. Pat. Nos. 5,889,128, 6,333,389 B2 and WO 00/37511.

The “Group 15-containing catalyst component” may comprise any combination of any “embodiment” described herein.

Phenoxide Transition Metal Catalyst Compositions

Phenoxide transition metal catalyst compositions are heteroatom substituted phenoxide ligated Group 3 to 10 transition metal or lanthanide metal compounds wherein the metal is bound to the oxygen of the phenoxide group. Phenoxide transition metal catalyst compounds may be represented by Formula XIX or XX:

wherein R¹ is hydrogen or a C₄ to C₁₀₀ group, preferably a tertiary alkyl group, preferably a C₄ to C₂₀ alkyl group, preferably a C₄ to C₂₀ tertiary alkyl group, preferably a neutral C₄ to C₁₀₀ group and may or may not also be bound to M;

at least one of R² to R⁵ is a heteroatom containing group, the rest of R² to R⁵ are independently hydrogen or a C₁ to C₁₀₀ group, preferably a C₄ to C₂₀ alkyl group, preferred examples of which include butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, isohexyl, octyl, isooctyl, decyl, nonyl, dodecyl, and any of R² to R⁵ also may or may not be bound to M;

Each R¹ to R⁵ group may be independently substituted or unsubstituted with other atoms, including heteroatoms or heteroatom containing group(s);

O is oxygen;

M is a Group 3 to Group 10 transition metal or lanthanide metal, preferably a Group 4 metal, preferably M is Ti, Zr or Hf;

n is the valence state of the metal M, preferably 2, 3, 4, or 5; and

Q is, and each Q may be independently be, an alkyl, halogen, benzyl, amide, carboxylate, carbamate, thiolate, hydride or alkoxide group, or a bond to an R group containing a heteroatom which may be any of R¹ to R⁵.

A heteroatom containing group may be any heteroatom or a heteroatom bound to carbon, silicon or another heteroatom. Preferred heteroatoms include boron, aluminum, silicon, nitrogen, phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, and tellurium. Particularly preferred heteroatoms include nitrogen, oxygen, phosphorus, and sulfur. Even more particularly preferred heteroatoms include nitrogen and oxygen. The heteroatom itself may be directly bound to the phenoxide ring or it may be bound to another atom or atoms that are bound to the phenoxide ring. The heteroatom containing group may contain one or more of the same or different heteroatoms. Preferred heteroatom containing groups include imines, amines, oxides, phosphines, ethers, ketones, oxoazolines heterocyclics, oxazolines, thioethers, and the like. Particularly preferred heteroatom containing groups include imines. Any two adjacent R groups may form a ring structure, preferably a 5 or 6 membered ring. Likewise the R groups may form multi-ring structures. In one embodiment any two or more R groups do not form a 5 membered ring.

In a preferred embodiment the heteroatom substituted phenoxide transition metal compound is an iminophenoxide Group 4 transition metal compound, and more preferably an iminophenoxidezirconium compound.

Supported Catalyst Systems

The activator and/or the polymerization catalyst compound may be combined with one or more support materials or carriers using any one of the support methods known in the art or as described below. In one embodiment the activator is in a supported form, for example deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, a support or carrier. In another embodiment, the activator and a catalyst compound may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, a support or carrier.

The terms “support” or “carrier” for purposes of this patent specification are used interchangeably and are any support material, preferably a porous support material, including inorganic or organic support materials. Non-limiting examples of inorganic support materials include inorganic oxides and inorganic chlorides. Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene, divinyl benzene, polyolefins, or polymeric compounds, zeolites, talc, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

In one embodiment, the heterocyclic compounds and the aluminum alkyl and/or the aluminoxanes described above are combined with one or more support materials or carriers. In another embodiment the heterocyclic compound is combined with a support material, preferably silica, treated with the alkylaluminum or the aluminoxane compound, such that the support has aluminum alkyl groups bonded thereto. The supported catalyst systems may be prepared, generally, by the reaction of the heterocyclic compound with an aluminum alkyl or aluminoxane, the addition of the catalyst precursor, followed by addition of a support material such as silica or alumina.

The support materials utilized may be any of the conventional support materials. Preferably the supported material is a porous support material, for example, talc, inorganic oxides and inorganic chlorides. Other support materials include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

The preferred support materials are inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports include silica, fumed silica, alumina, silica-alumina and mixtures thereof. Other useful supports include magnesia, titania, zirconia, magnesium chloride, montmorillonite, phyllosilicate, zeolites, talc, clays and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania and the like. Additional support materials may include those porous acrylic polymers. Other support materials include nanocomposites, aerogels, spherulites, and polymeric beads. Another support is fumed silica available under the trade name Cabosil™ TS-610, available from Cabot Corporation. Fumed silica is typically a silica with particles 7 to 30 nanometers in size that has been treated with dimethylsilyldichloride such that a majority of the surface hydroxyl groups are capped.

In another embodiment, any of the conventionally known inorganic oxides, such as silica, support materials that retain hydroxyl groups after dehydration treatment methods will be suitable in accordance with the invention. Because of availability, both of silica and silica containing metal oxide based supports, for example, silica-alumina, are preferred. Silica particles, gels and glass beads are most typical.

These metal oxide compositions may additionally contain oxides of other metals, such as those of Al, K, Mg, Na, Si, Ti and Zr and should preferably be treated by thermal and/or chemical means to remove water and free oxygen. Typically such treatment is in a vacuum in a heated oven, in a heated fluidized bed or with dehydrating agents such as organo silanes, siloxanes, alkyl aluminum compounds, etc. The level of treatment should be such that as much retained moisture and oxygen as is possible is removed, but that a chemically significant amount of hydroxyl functionality is retained. Thus calcining at up to 800° C. or more up to a point prior to decomposition of the support material, for several hours is permissible, and if higher loading of supported anionic activator is desired, lower calcining temperatures for lesser times will be suitable. Where the metal oxide is silica, loadings to achieve from less than 0.1 mmol to 3.0 mmol activator/g SiO₂ are typically suitable and can be achieved, for example, by varying the temperature of calcining from 200° C. to 1,000° C., such as from 300° C. to 900° C., 400° C. to 875° C., 500° C. to 850° C., 600° C., to 825° C., 700° C. to 800° C., and any combination of any limit with any lower limit.

The tailoring of hydroxyl groups available as attachment sites in this invention can also be accomplished by the pre-treatment with a less than stoichimetric amount of a chemical dehydrating agent. If calcining temperatures below 400° C. are employed, difunctional coupling agents (e.g., (CH₃)₃SiCl₂) may be employed to cap hydrogen bonded pairs of silanol groups which are present under the less severe calcining conditions. Similarly, use of the Lewis acid in excess of the stoichimetric amount needed for reaction with the transition metal compounds will serve to neutralize excess silanol groups without significant detrimental effect for catalyst preparation or subsequent polymerization.

In another embodiment, the support is a polymeric support, including hydroxyl-functional-group-containing polymeric substrates, but functional groups may be any of the primary alkyl amines, secondary alkyl amines, and others, where the groups are structurally incorporated in a polymeric chain and capable of a acid-base reaction with the Lewis acid such that a ligand filling one coordination site of the aluminum is protonated and replaced by the polymer incorporated functionality. See, for example, the functional group containing polymers of U.S. Pat. No. 5,288,677.

It is preferred that the support material, most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 μm. More preferably, the surface area of the support material is in the range of from about 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 μm. The average pore size of the carrier is typically in the range of from 10 to 1000 Å, preferably 50 to about 500 Å, and most preferably 75 to about 350 Å.

The support materials may be treated chemically, for example with a fluoride compound as described in WO 00/12565. Other supported activators are described in for example WO 00/13792 that refers to supported boron containing solid acid complex.

In one embodiment, the support material having an alkylaluminum and/or the aluminoxane compound bonded thereto may be prepared by combining the aluminum containing compound with the support material in a suitable solvent. In one embodiment, the combining is carried out at any suitable pressure and temperature under an inert atmosphere. Preferably the combining is at atmospheric pressure, ambient temperature under nitrogen. More preferably the mixture is heated to less than about 200° C., more preferably less than 150° C. The reactants are contacted for a suitable about of time for example, for at least about 1 minute, preferably about 1 minute to about 10 hours, more preferably for about 1 minute to about 3 hours.

In another embodiment, an antistatic agent or surface modifier that is used in the preparation of the supported catalyst system as described in PCT publication WO 96/11960 may be used with catalyst systems including the activator compounds described herein. The catalyst systems may also be prepared in the presence of an olefin, for example 1-hexene.

In another embodiment, the activator and/or catalyst system may be combined with a carboxylic acid salt of a metal ester, for example aluminum carboxylates such as aluminum mono, di- and tri-stearates, aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S. Pat. Nos. 6,300,436 and 6,306,984.

In another embodiment there is a method for producing a supported metallocene-type catalyst system, which maybe used to support the activator described herein. In this method, the catalyst compound is slurried in a liquid to form a catalyst solution or emulsion. A separate solution is formed containing the activator. The liquid may be any compatible solvent or other liquid capable of forming a solution or the like with the catalyst compounds and/or activator. In the most preferred embodiment the liquid is a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene. The catalyst compound and activator solutions are mixed together heated and added to a heated porous support or a heated porous support is added to the solutions such that the total volume of the metallocene-type catalyst compound solution and the activator solution or the metallocene-type catalyst compound and activator solution is less than four times the pore volume of the porous support, more preferably less than three times, even more preferably less than two times; preferred ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range.

In one embodiment, a method of forming a supported catalyst system, the amount of liquid, in which the activator and/or a catalyst compound is present, is in an amount that is less than four times the pore volume of the support material, more preferably less than three times, even more preferably less than two times; preferred ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range. In an alternative embodiment, the amount of liquid in which the activator is present is from one to less than one times the pore volume of the support material utilized in forming the supported activator.

In one embodiment, the amount of heterocyclic nitrogen-containing compound ranges from 0.05 equivalents to 10.0 equivalents per equivalent of alkylaluminum. In another embodiment, the amount of heterocyclic nitrogen-containing compound ranges from 0.2 equivalents to 5.0 equivalents per equivalent of alkylaluminum. In yet another embodiment, the amount of heterocyclic nitrogen-containing compound ranges from 1.0 equivalents to 4.0 equivalents per equivalent of alkylaluminum.

Polymerization Process

The activators and catalysts described above, whether supported or not, are suitable for use in any prepolymerization and/or polymerization process over a wide range of temperatures and pressures. The temperatures may be in the range of from −60° C. to about 280° C., preferably from 50° C. to about 200° C. In one embodiment, the polymerization temperature is above 0° C., above 50° C., above 80° C., above 100° C., above 150° C., or above 200° C. In one embodiment, the pressures employed may be in the range from 1 atmosphere to about 500 atmospheres or higher.

Polymerization processes include solution, gas phase, slurry phase, and a high pressure process, or a combination thereof. Particularly preferred is a gas phase or slurry phase polymerization of one or more olefin(s) at least one of which is ethylene or propylene.

In one embodiment, the process is a solution, high pressure, slurry or gas phase polymerization process of one or more olefin monomers having from 2 to 30 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably 2 to 8 carbon atoms. The invention is particularly well suited to the polymerization of two or more olefin monomers of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene.

Other monomers useful include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins. Non-limiting monomers useful in the invention may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene.

In another embodiment, a copolymer of ethylene is produced, where with ethylene, a comonomer having at least one alpha-olefin having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms, is polymerized in a gas phase process.

In another embodiment, ethylene or propylene is polymerized with at least two different comonomers, optionally one of which may be a diene, to form a terpolymer.

In one embodiment, the invention is directed to a polymerization process, particularly a gas phase or slurry phase process, for polymerizing propylene alone or with one or more other monomers including ethylene, and/or other olefins having from 4 to 12 carbon atoms.

Typically in a gas phase polymerization process, a continuous cycle is employed where in one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system external to the reactor. Generally, in a gas fluidized bed process for producing polymers, a gaseous stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back into the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer.

The reactor pressure in a gas phase process may vary from about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the range of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably in the range of from about 250 psig (1724 kPa) to about 350 psig (2414 kPa).

The reactor temperature in a gas phase process may vary from about 30° C. to about 120° C., preferably from about 60° C. to about 115° C., more preferably in the range of from about 70° C. to 110° C., and most preferably in the range of from about 70° C. to about 95° C. In another embodiment, the reactor temperature in a gas phase process is above 60° C.

Other gas phase processes include series or multistage polymerization processes. Gas phase processes may also include those described in U.S. Pat. Nos. 5,627,242, 5,665,818 and 5,677,375, and European publications EP-A-0 794 200 EP-B1-0 649 992, EP-A-0 802 202 and EP-B-634 421.

In another embodiment, the process may produce greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greater than 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr).

A slurry polymerization process generally uses pressures in the range of from about 1 to about 50 atmospheres and even greater and temperatures in the range of 0° C. to about 120° C. In another embodiment, the slurry process temperature is above 100° C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen along with catalyst are added. The suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor. The liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, preferably a branched alkane. The medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used the process must be operated above the reaction diluent critical temperature and pressure. Preferably, a hexane or an isobutane medium is employed.

In another embodiment, the polymerization technique is referred to as a particle form polymerization, or a slurry process where the temperature is kept below the temperature at which the polymer goes into solution. Such technique is well known in the art, and described in for instance U.S. Pat. No. 3,248,179 which is fully incorporated herein by reference. Other slurry processes include those employing a loop reactor and those utilizing a plurality of stirred reactors in series, parallel, or combinations thereof. Non-limiting examples of slurry processes include continuous loop or stirred tank processes. Also, other examples of slurry processes are described in U.S. Pat. No. 4,613,484, which is herein fully incorporated by reference.

In another embodiment, this process may produce greater than 2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than 5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr (4540 Kg/hr). In another embodiment the slurry reactor may produce greater than 15,000 lbs of polymer per hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340 Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

Examples of solution processes are described in U.S. Pat. Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555 and PCT WO 99/32525.

In one embodiment, the slurry or gas phase process is operated in the presence of the catalyst system described herein and in the absence of or essentially free of any scavengers, such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like. This process is described in PCT publication WO 96/08520 and U.S. Pat. Nos. 5,712,352 and 5,763,543.

In another embodiment, the method provides for injecting the catalyst system described herein into a reactor, particularly a gas phase reactor. In one embodiment the catalyst system is used in the unsupported form, preferably in a liquid form such as described in U.S. Pat. Nos. 5,317,036 and 5,693,727 and European publication EP-A-0 593 083. The polymerization catalyst in liquid form can be fed with an activator, and/or a support, and/or a supported activator together or separately to a reactor. The injection methods described in PCT publication WO 97/46599 may be utilized.

Where an unsupported catalyst system is used the mole ratio of the metal of the activator component to the metal of the catalyst compound is in the range of between 0.3:1 to 10,000:1, preferably 100:1 to 5000:1, and most preferably 500:1 to 2000:1.

Polymer Products

The polymers produced can be used in a wide variety of products and end-use applications. The polymers produced include linear low density polyethylene, elastomers, plastomers, high density polyethylenes, medium density polyethylenes, low density polyethylenes, polypropylene and polypropylene copolymers.

The polymers, typically ethylene based polymers, have a density in the range of from 0.86 g/cc to 0.97 g/cc, preferably in the range of from 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to 0.940 g/cc, and most preferably greater than 0.915 g/cc, preferably greater than 0.920 g/cc, and most preferably greater than 0.925 g/cc. Density is measured in accordance with ASTM-D-1238.

The polymers produced typically have a molecular weight distribution, a weight average molecular weight to number average molecular weight (M_(w)/M_(n)) of greater than 1.5 to about 15, particularly greater than 2 to about 10, more preferably greater than about 2.2 to less than about 8, and most preferably from 2.5 to 8. The polymers may have a narrow molecular weight distribution and a broad composition distribution or vice-versa, and may be those polymers described in U.S. Pat. No. 5,798,427.

Also, the polymers typically have a narrow composition distribution as measured by Composition Distribution Breadth Index (CDBI). Further details of determining the CDBI of a copolymer are known to those skilled in the art. See, for example, PCT Patent Application WO 93/03093, published Feb. 18, 1993. The polymers in one embodiment have CDBI's generally in the range of greater than 50% to 100%, preferably 99%, preferably in the range of 55% to 85%, and more preferably 60% to 80%, even more preferably greater than 60%, still even more preferably greater than 65%. In another embodiment, polymers produced using a catalyst system described herein have a CDBI less than 50%, more preferably less than 40%, and most preferably less than 30%.

The polymers in one embodiment have a melt index (MI) or (I₂) as measured by ASTM-D-1238-E (190/2.16) in the range from no measurable flow to 1000 dg/min, more preferably from about 0.01 dg/min to about 100 dg/min, even more preferably from about 0.1 dg/min to about 50 dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min.

In one embodiment, the polymers have a melt index ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) (190/21.6) of from 10 to less than 25, more preferably from about 15 to less than 25. The polymers, in a preferred embodiment, have a melt index ratio (I₂₁/I₂) of from greater than 25, more preferably greater than 30, even more preferably greater that 40, still even more preferably greater than 50 and most preferably greater than 65. For example, the melt index ratio (I₂₁/I₂) may be of from 5 to 300, 10 to 200, 20 to 180, 30 to 160, 40 to 120, 50 to 100, 60 to 90, and a combination of any upper limit with any lower limit.

In yet another embodiment, propylene based polymers are produced. These polymers include atactic polypropylene, isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene. Other propylene polymers include propylene block or impact copolymers. Propylene polymers of these types are well known in the art see for example U.S. Pat. Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and 5,459,117.

The polymers may be blended and/or coextruded with any other polymer. Non-limiting examples of other polymers include linear low density polyethylenes, elastomers, plastomers, high pressure low density polyethylene, high density polyethylenes, polypropylenes and the like.

The polymers produced and blends thereof are useful in such forming operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding. Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc. in food-contact and non-food contact applications. Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc. Extruded articles include medical tubing, wire and cable coatings, pipe, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.

EXAMPLES

In order to provide a better understanding, the following non-limiting examples are offered. In each of the examples to follow: indole and 4-flouroindole were purchased from Aldrich and used as received; anhydrous toluene and pentane were purchased from Aldrich and dried overnight over a sodium potassium alloy; 5-Bromoindole and 5-chloroindole were purchased from Biosynth Biochemica & Synthetica and used as received; (1,3-MeBuCp)₂Zr-Me₂, 20 wt % solution in toluene was purchased from Norquay Single-Site Catalysts and used as received; and 4,5,6,7-tetrafluoroindole was purchased from Matrix and used as received.

Example 1

In a 100 mL round bottom flask, 2-methylindole (1.0 grams) was combined with triethylaluminum (0.434 grams) in toluene (40 mls). Ethane evolution from the solution was observed. The solution was heated for 70 minutes at 100° C. The solution was then cooled to room temperature, and concentrated to a thick oil. Tan crystals grew from the solution on the bottom of the flask. A proton NMR study revealed that the crystal contained the following molecule: [NC₈H₅(CH₃)][NC₈H₆(CH₃)]Al[C₂H₅]₂

¹H NMR (C₆D₆): δ 0.66 & 0.72 (overlapping quartets), 1.30 (t), 1.44 (s), 2.22 (s), 2.51(s), 6.55 (s), 6.75 (d), 6.87 (m), 7.04 (m), 7.54 (d), 7.77 (m).

A crystallography of the crystals was also performed. Single crystals of [NC₈H₅(CH₃)][NC₈H₆(CH₃)]Al[C₂H₅]₂ were subjected to X-rays by Victor Day at Crystalytics, located in Lincoln, Nebr. The X-ray structure determination revealed a neutral four-coordinate aluminum center. One ethyl moiety of the parent triethylaluminum was protonated off via one equivalent of 2-methylindole. The second equivalent of 2-methyl-indole was coordinated to the aluminum center. The proton of the indole was determined to have migrated to the 3 position of the indole yielding a —CH₂— group. The proton migration resulted in a shortening of the N21-C22 bond 1.313(5)A compared to the other indole ligand N11-C12 bond (1.393(5) A). An ORTEP of the structure is displayed in FIG. 1 a and a ball and stick perspective drawing of the solid-state structure is shown in FIG. 1 b. Atomic Coordinates for Nonhydrogen Atoms are listed in Table 1, and the Anisotropic Thermal Parameters are listed in Table 2. Atomic Coordinates for Hydrogen Atoms are listed in Table 3. Selected bond lengths are shown in Table 4 and selected bond angles are shown in Table 5. Selected torsion angles are shown in Table 6.

TABLE 1 Atomic Coordinates for Nonhydrogen Atoms in Crystalline [NC₈H₅(CH₃)][NC₈H₆(CH₃)]Al[C₂H₅]₂ ^(a) Atom Fraction Coordinates Equivalent Isotropic Thermal Type^(b) 10⁴x 10⁴y 10⁴z Parameter U, {acute over (Å)}² × 10³c Al 3302(1) 2000(1) 5858(2) 31(1) N₁₁ 3287(2) 3065(2) 6897(4) 30(1) N₂₁ 2533(2) 2182(2) 3231(5) 26(1) C₁ 2730(4) 1226(4) 7050(7) 44(1) C₂ 3167(4) 1301(3) 9178(6) 55(2) C₃ 4395(3) 1635(4) 5642(8) 39(1) C₄ 4267(4)  874(3) 4448(8) 76(2) C₁₂ 3973(3) 3490(3) 8172(6) 29(1) C₁₃ 3672(3) 4167(3) 8877(6) 36(1) C₁₄ 2096(3) 4677(3) 8243(7) 39(1) C₁₅ 1260(3) 4510(3) 7192(7) 38(1) C₁₆ 1050(4) 3842(3) 5969(7) 41(1) C₁₇ 1685(3) 3331(3) 5790(6) 35(1) C₁₈ 2540(3) 3490(3) 6840(5) 26(1) C₁₉ 2762(3) 4178(3) 8047(6) 32(1) C₂₀ 4887(3) 3225(3) 8650(6) 39(1) C₂₂ 2525(3) 2852(3) 2267(6) 30(1) C₂₃ 1767(4) 2862(3)  506(7) 41(1) C₂₄  695(3) 1638(4) −799(7) 38(1) C₂₅  503(3)  848(4) −424(7) 43(2) C₂₆  986(3)  447(3) 1223(6) 40(1) C₂₇ 1657(3)  864(3) 2514(6) 31(1) C₂₈ 1838(3) 1654(3) 2151(5) 24(1) C₂₉ 1369(3) 2040(3)  485(6) 30(1) C₃₀ 3191(3) 3502(3) 2810(6) 41(1) ^(a)The numbers in parentheses are the estimated standard deviations in the last significant digit. ^(b)Atoms are labeled in agreement with FIG. 1A. ^(c)This is one-third of the trace of the orthogonalized U_(ij) tensor.

TABLE 2 Anisotropic Thermal Parameters for Nonhydrogen Atoms in Crystalline [NC₈H₅(CH₃)][NC₈H₆(CH₃)]Al[C₂H₅]₂ ^(a,b) Atom Anisotropic Thermal Parameters ({acute over (Å)}² × 10³c) Type^(c) U₁₁ U₂₂ U₃₃ U₂₃ U₁₃ U₁₂ Al 34(1) 34(1) 26(1) 1(1) 13(1) 0(1) N₁₁ 24(2) 39(2) 27(2) −5(2) 10(2) −6(2) N₂₁ 24(2) 31(2) 28(2) −5(2) 15(2) −4(2) C₁ 52(4) 48(4) 37(3) 6(3) 22(3) −2(3) C₂ 70(4) 67(4) 33(3) 12(2) 25(3) 4(3) C₃ 36(3) 39(4) 43(3) −8(3) 14(3) −3(3) C₄ 55(4) 86(5) 85(5) −29(4) 22(4) 19(4) C₁₂ 28(3) 36(3) 21(2) 1(2) 6(2) −10(2) C₁₃ 42(3) 36(3) 25(3) −7(2) 7(3) −16(3) C₁₄ 53(4) 40(3) 32(3) −8(3) 25(3) 2(3) C₁₅ 40(4) 38(3) 40(3) 4(3) 21(3) 6(3) C₁₆ 31(3) 57(4) 34(3) −1(3) 12(3) 3(3) C₁₇ 37(3) 43(3) 25(3) −4(3) 12(3) 4(3) C₁₈ 28(3) 29(3) 22(3) 3(2) 12(2) −1(2) C₁₉ 40(4) 32(3) 25(3) 7(2) 13(3) −4(3) C₂₀ 34(3) 53(3) 31(3) −7(2) 12(2) −4(3) C₂₂ 40(3) 31(3) 27(3) −1(2) 21(3) 2(3) C₂₃ 51(4) 54(4) 26(3) 4(3) 22(3) 5(3) C₂₄ 37(3) 49(4) 32(3) 0(3) 17(3) 3(3) C₂₅ 32(4) 60(4) 35(3) −16(3) 12(3) −10(3) C₂₆ 51(4) 37(3) 41(4) −6(3) 26(3) −3(3) C₂₇ 33(3) 33(3) 27(3) −8(3) 9(3) 0(3) C₂₈ 28(3) 27(3) 21(3) −9(2) 12(2) 2(2) C₂₉ 33(3) 37(3) 24(3) −4(2) 17(2) 0(3) C= 56(3) 40(3) 39(3) 5(2) 30(3) 0(3) ^(a)The numbers in parentheses are the estimated standard deviations in the last significant digit. ^(b)The form of the anisotropic thermal parameter is: exp[−2_(Π) ²(U₁₁h²a*² + U₂₂k²b*² + U331²c*² + 2U₁₂hka*b* + 2U₁₃hla*c* + 2U₂₃klb*c*)]. ^(c)Atoms are labeled in agreement with FIG. 1A.

TABLE 3 Atomic Coordinates for Hydrogen Atoms in Crystalline [NC₈H₅(CH₃)][NC₈H₆(CH₃)]Al[C₂H₅]₂ ^(a,b) Atom Fraction Coordinates Isotropic Thermal Type^(c) 10⁴x 10⁴y 10⁴z Parameter, {acute over (Å)}² × 10³ H_(1a) 2070(30) 1360(30)  6660(70)  73(17) H_(1b) 2740(30)  570(30)  6840(60)  64(16) H_(2a) 2879  928  9771  82 H_(2b) 3121 1874  9553  82 H_(2c) 3777 1147  9549  82 H_(3a) 4700(30) 2050(20)  5550(60)  35(15) H_(3b) 4890(30) 1490(30)  6930(70)  56(15) H_(4a) 4824  696  4403 114 H_(4b) 3872 1004  3202 114 H_(4c) 4023  427  4963 114 H₁₃ 4040(20) 4590(20)  9790(50)  15(10) H₁₄ 2260(20) 5080(20)  9320(60)  46(13) H₁₅  810(20) 4920(20)  7390(50)  37(12) H₁₆  430(20) 3770(20)  5200(50)  19(11) H₁₇ 1520(20) 2860(20)  5030(50)  21(12) H_(20a) 5269 3633  9482  58 H_(20b) 5022 3186  7526  58 H_(20c) 4972 2682  9256  58 H_(23a) 1400(30) 3400(30)  330(60)  63(16) H_(23b) 1920(20) 2900(20)  −360(50)  17(12) H₂₄  370(30) 2040(30) −1750(60)  61(16) H₂₅  60(30)  550(30) −1250(60)  53(16) H₂₆  920(20) −170(20)  1360(50)  36(13) H₂₇ 2040(20)  570(20)  3430(50)  33(14) H_(30a) 3534 3448  4123  62 H_(30b) 2915 4050  2577  62 H_(30c) 3567 3443  2093  62 ^(a)Hydrogen atoms were located from a difference Fourier. The four methyl groups (C₂, C₄, C₂₀, C₃₀ and their hydrogens) were eventually refined as rigid rotors (using idealized sp³-hybridized geometry and a C—H bond length of 0.98 {acute over (Å)}) which were allowed to rotate around their respective C—C bonds in least-squares cycles. The remaining hydrogen atoms were included in the structural model as individual # isotropic atoms whose parameters were refined. The isotropic thermal parameters of all methyl hydrogen atoms were fixed at values 1.5 times the equivalent isotropic thermal parameter of the carbon atom to which they are covalently bonded. ^(b)The numbers in parentheses are the estimated standard deviations in the last significant digit for parameters which are refined. ^(c)Hydrogen atoms are labeled with the same numerical subscript(s) as the carbon atoms to which they are covalently bonded and carry an additional literal subscript (a, b or c) where necessary to distinguish between hydrogens bonded to the same carbon.

TABLE 4 Bond Lengths in Crystalline [NC₈H₅(CH₃)][NC₈H₆(CH₃)]Al[C₂H₅]₂ ^(a) Type^(b) Length, {acute over (Å)} Type^(b) Length, {acute over (Å)} Al—N₁₁ 1.901(4) Al—N₂₁ 2.009(4) Al—C₁ 1.988(5) Al—C₃ 1.971(5) C₁-C₂ 1.558(6) C₃-C₄ 1.508(6) N₁₁—C₁₂ 1.393(5) N₂₁—C₂₂ 1.313(5) N₁₁—C₁₈ 1.403(5) N₂₁—C₂₈ 1.438(5) C₁₂-C₁₃ 1.392(6) C₂₂-C₂₃ 1.495(6) C₁₂-C₂₀ 1.491(6) C₂₂-C₃₀ 1.471(6) C₁₃-C₁₉ 1.415(6) C₂₃-C₂₉ 1.478(6) C₁₄-C₁₅ 1.363(6) C₂₄-C₂₅ 1.369(6) C₁₄-C₁₉ 1.420(6) C₂₄-C₂₉ 1.368(6) C₁₅-C₁₆ 1.397(6) C₂₅-C₂₆ 1.404(7) C₁₆-C₁₇ 1.384(6) C₂₆-C₂₇ 1.379(6) C₁₇-C₁₈ 1.386(6) C₂₇-C₂₈ 1.362(6) C₁₈-C₁₉ 1.414(6) C₂₈-C₂₉ 1.397(6) C₁—H_(1a)  1.05(5) C₃—H_(3a)  0.86(4) C₁—H_(1b)  1.07(5) C₃—H_(3b)  1.07(5) C₁₄—H₁₄  1.01(4) C₂₄—H₂₄  0.98(5) C₁₅—H₁₅  1.05(4) C₂₅—H₂₅  0.92(4) C₁₆—H₁₆  1.00(3) C₂₆—H₂₆  1.01(4) C₁₇—H₁₇  0.94(3) C₂₇—H₂₇  0.90(4) C₁₃—H₁₃  1.01(3) C₂₃—H_(23a)  1.03(5) C₂₃—H_(23b)  0.80(4) ^(a)The numbers in parentheses are the estimated standard deviations in the last significant digit. ^(b)Atoms are labeled in agreement with FIG. 1A.

TABLE 5 Bond Angles in Crystalline [NC₈H₅(CH₃)][NC₈H₆(CH₃)]Al[C₂H₅]₂ ^(a) Type^(b) Angle, (deg) Type^(b) Angle, (deg) N₁₁AlN₂₁ 101.6(2) C₁AlN₂₁ 109.3(2) N₁₁AlC₁ 106.6(2) C₃AlN₂₁ 103.1(2) N₁₁AlC₃ 117.3(2) C₃AlC₁ 117.5(3) C₁₂N₁₁Al 127.9(3) C₂₂N₂₁Al 125.1(3) C₁₈N₁₁Al 124.9(3) C₂₈N₂₁Al 126.5(3) C₁₂N₁₁C₁₈ 105.8(3) C₂₂N₂₁C₂₈ 108.1(4) C₂C₁Al 109.2(4) C₄C₃Al 111.4(4) AlC₁H_(1a)   111(3) AlC₃H_(3a)   111(3) AlC₁H_(1b)   121(2) AlC₃H_(3b)   114(2) C₂C₁H_(1a)   110(3) C₄C₃H_(3a)   123(3) C₂C₁H_(1b)   102(2) C₄C₃H_(3b)   107(2) H_(1a)C₁H_(1b)   104(4) H_(3a)C₃H_(3b)   89(3) C₁₃C₁₂N₁₁ 110.4(4) N₂₁C₂₂C₂₃ 111.5(4) N₁₁C₁₂C₂₀ 122.5(4) N₂₁C₂₂C₃₀ 124.7(4) C₁₃C₁₂C₂₀ 127.1(4) C₃₀C₂₂C₂₃ 123.8(4) C₁₂C₁₃C₁₉ 107.8(4) C₂₉C₂₃C₂₂ 103.1(4) C₁₂C₁₃H₁₃   126(2) C₂₂C₂₃H_(23a)   113(3) C₁₉C₁₃H₁₃   126(2) C₂₂C₂₃H_(23b)   111(3) C₂₉C₂₃H_(23a)   121(3) C₂₉C₂₃H_(23b)   110(3) H_(23a)C₂₃H_(23b)   99(4) C₁₅C₁₄C₁₉ 119.4(5) C₂₉C₂₄C₂₅ 118.4(5) C₁₄C₁₅C₁₆ 120.9(5) C₂₄C₂₅C₂₆ 121.5(5) C₁₇C₁₆C₁₅ 120.9(5) C₂₇C₂₆C₂₅ 119.4(5) C₁₆C₁₇C₁₈ 119.2(5) C₂₈C₂₇C₂₆ 119.0(5) C₁₇C₁₈N₁₁ 129.5(4) C₂₇C₂₈N₂₁ 128.5(4) N₁₁C₁₈C₁₉ 110.1(4) C₂₉C₂₈N₂₁ 110.2(4) C₁₇C₁₈C₁₉ 120.4(4) C₂₇C₂₈C₂₉ 121.2(4) C₁₃C₁₉C₁₄ 134.8(4) C₂₄C₂₉C₂₃ 132.6(4) C₁₈C₁₉C₁₃ 106.0(4) C₂₈C₂₉C₂₃ 106.9(4) C₁₈C₁₉C₁₄ 119.1(4) C₂₄C₂₉C₂₈ 120.5(5) C₁₅C₁₄H₁₄   123(2) C₂₅C₂₄H₂₄   131(3) C₁₉C₁₄H₁₄   117(2) C₂₉C₂₄H₂₄   109(3) C₁₄C₁₅H₁₅   115(2) C₂₄C₂₅H₂₅   122(3) C₁₆C₁₅H₁₅   124(2) C₂₆C₂₅H₂₅   117(3) C₁₅C₁₆H₁₆   116(2) C₂₅C₂₆H₂₆   120(2) C₁₇C₁₆H₁₆   123(2) C₂₇C₂₆H₂₆   119(2) C₁₆C₁₇H₁₇   118(2) C₂₆C₂₇H₂₇   118(3) C₁₈C₁₇H₁₇   122(2) C₂₈C₂₇H₂₇   121(3) ^(a)The numbers in parentheses are the estimated standard deviations in the last significant digit. ^(b)Atoms are labeled in agreement with FIG. 1A.

TABLE 6 Torsion Angles in Crystalline [NC₈H₅(CH₃)][NC₈H₆(CH₃)]Al[C₂H₅]₂ ^(a) Angle, Type^(b) Angle, (deg) Type^(b) (deg) C₃—Al—N₁₁—C₁₂ −28.4(4) Al—N₁₁—C₁₈-C₁₉ 168.2(3) C₁—Al—N₁₁—C₁₂ 105.7(4) C₁₇-C₁₈-C₁₉-C₁₃ −179.3(4) N₂₁—Al—N₁₁—C₁₂ −139.9(3) N₁₁—C₁₈-C₁₉-C₁₃ −0.6(5) C₃—Al—N₁₁—C₁₈ 167.2(4) C₁₇-C₁₈-C₁₉-C₁₄ 3.3(6) C₁—Al—N₁₁—C₁₈ −58.7(4) N₁₁—C₁₈-C₁₉-C₁₄ −177.9(4) N₂₁—Al—N₁₁—C₁₈ 55.7(3) C12-C₁₃-C₁₉-C₁₈ 0.0(5) N₁₁—Al—N₂₁—C₂₂ 40.0(4) C12-C₁₃-C₁₉-C₁₄ 176.7(5) C₃—Al—N₂₁—C₂₂ −81.8(4) C15-C₁₄-C₁₉-C₁₈ −3.5(6) C₁—Al—N₂₁—C₂₂ 152.5(4) C15-C₁₄-C₁₉-C₁₃  −179.(5) N₁₁—Al—N₂₁—C₂₈ −132.6(3) C₂₈—N₂₁—C₂₂-C₃₀ −173.1(4) C₃—Al—N₂₁—C₂₈ 105.6(3) Al—N₂₁—C₂₂-C₃₀ 13.2(6) C₁—Al—N₂₁—C₂₈ −20.1(4) C₂₈—N₂₁—C₂₂-C₂₃ 5.1(5) N₁₁—Al—C₁-C₂ −53.0(4) Al—N₂₁—C₂₂-C₂₃ −168.6(3) C₃—Al—C₁-C₂ 81.0(4) N₂₁—C₂₂-C₂₃-C₂₉ −5.7(5) N₂₁—Al—C₁-C₂ −162.1(3) C₃₀-C₂₂-C₂₃-C₂₉ 172.4(4) N₁₁—Al—C₃-C₄ −167.9(4) C₂₉-C₂₄-C₂₅-C₂₆ −0.6(7) C₁—Al—C₃-C₄ 62.9(5) C₂₄-C₂₅-C₂₆-C₂₇ 1.4(7) N₂₁—Al—C₃-C₄ −57.3(5) C₂₅-C₂₆-C₂₇-C₂₈ −0.4(7) C₁₈—N₁₁—C₁₂-C₁₃ −0.9(5) C₂₆-C₂₇-C₂₈-C₂₉ −1.4(7) Al—N₁₁—C₁₂-C₁₃ −167.6(3) C₂₆-C₂₇-C₂₈—N₂₁ −175.7(4) C₁₈—N₁₁—C₁₂-C₂₀ 179.3(4) C₂₂—N₂₁—C₂₈-C₂₇ 172.5(4) Al—N₁₁—C₁₂-C₂₀ 12.6(6) Al—N₂₁—C₂₈-C₂₇ −13.9(6) N₁₁—C₁₂-C₁₃-C₁₉ 0.6(5) C₂₂—N₂₁—C₂₈-C₂₉ −2.4(5) C₂₀-C₁₂-C₁₃-C₁₉ −179.7(4) Al—N₂₁—C₂₈-C₂₉ 171.2(3) C₁₉-C₁₄-C₁₅-C₁₆ 1.9(7) C₂₅-C₂₄-C₂₉-₂₈ −1.2(6) C₁₄-C₁₅-C₁₆-C₁₇ 0.0(7) C₂₅-C₂₄-C₂₉-C₂₃ 177.3(5) C₁₅-C₁₆-C₁₇-C₁₈ −0.2(7) C₂₇-C₂₈-C₂₉-C₂₄ 2.2(6) C₁₆-C₁₇-C₁₈—N₁₁ −180.0(4) N₂₁—C₂₈-C₂₉-C₂₄ 177.5(4) C₁₆-C₁₇-C₁₈-C₁₉ −1.5(6) C₂₇-C₂₈-C₂₉-C₂₃ −176.6(4) C₁₂—N₁₁—C₁₈-C₁₇ 179.5(4) N₂₁—C₂₈-C₂₉-C₂₃ −1.3(5) Al—N₁₁—C₁₈-C₁₇ −13.2(6) C₂₂-C₂₃-C₂₉-C₂₄ −174.6(5) C₁₂—N₁₁—C₁₈-C₁₉ 0.9(4) C₂₂-C₂₃-C₂₉-C₂₈ 4.0(5) ^(a)The numbers in parentheses are the estimated standard deviations in the last significant digit. ^(b)Atoms are labeled in agreement with FIG. 1A.

Example 2

Preparation of [NC₈H₆][NC₈H₇]Al[C₂H₅]₂: In a 100 mL round bottom flask, indole (1.0 grams) was combined with triethylaluminum (0.487 grams) in toluene (40 mls). Vigorous ethane evolution from the solution (yellow-green) was observed. After several hours, conversion to the title species had occurred. [NC₈H₆][NC₈H₇]Al[C₂H₅]₂ was identified by proton NMR. ¹H NMR (C₆D₆): δ 0.68 (m), 1.43 (t), 2.0 (s), 6.6 (d), 6.8 (m), 6.9, 7.04 (m), 7.2 (m), 7.6 (m), 7.95 (m).

Example 3

Preparation of [NC₈H₅F][NC₈H₆F]Al[C₂H₅]₂: In a 100 mL round bottom flask, 4-fluoroindole (1.0 grams) was combined with triethylaluminum (0.422 grams) benzene (C₆D₆) (20 mls). Ethane evolution from the solution was observed. After six hours, conversion to title species had largely taken place. [NC₈H₅F][NC₈H₆F]Al[C₂H₅]₂ was identified by proton NMR and fluorine NMR. ¹H NMR (C₆D₆): δ 0.58 (m), 1.49 (t), 2.0 (s), 6.5-7.6. ¹⁹F NMR: δ −115.8, −121.7. Ethane, δ 0.791 (s).

Example 4

Preparation of [NC₈H₅Br][NC₈H₆Br]Al[C₂H₅]₂: In a 100 mL round bottom flask, 5-bromoindole (0.822 grams) was combined with triethylaluminum (0.239 grams) benzene (C₆D₆) (20 mls). Ethane evolution from the solution was observed. After two hours, conversion to the title species had largely taken place. [NC₈H₅Br][NC₈H₆Br]Al[C₂H₅]₂ was identified by proton NMR. ¹H NMR (C₆D₆): δ 0.587 (m), 1.34 (t), 1.83 (s), 6.59, 6.71, 6.8, 7.11, 7.34, 7.51, 8.06. Ethane, δ 0.791 (s).

Example 5

Preparation of [NC₈H₂F₄][NC₈H₃F₄]Al[C₂H₅]₂: In a 100 mL round bottom flask, 4,5,6,7-tetrafluoroindole (1.0 grams) was combined with triethylaluminum (0.301 grams) benzene (C₆D₆) (20 mls). Ethane evolution from the solution was observed. After two hours, conversion to the title species had largely taken place. [NC₈H₂F₄][NC₈H₃F₄]Al[C₂H₅]₂ was identified by proton NMR. ¹H NMR (C₆D₆): δ 0.54 (m), 1.25 (t), 2.16 (s), 6.8, 7.39, 7.53. Ethane, δ 0.791 (s).

Example 6

Preparation of [NC₈H₅(CH₃)]₂[NC₈H₆(CH₃)]Al[C₂H₅]: In a 100 mL round bottom flask, 3-methylindole (1.0 grams) was combined with triethylaluminum (0.29 grams) in toluene (20 mls). Ethane evolution from the solution was observed. The solution was heated for four hours at 50 C. A first portion of the yellow solution was cooled to room temperature, and a second portion was left at room temperature for two days. A yellow powder formed. The yellow powder was filtered and rinsed with pentane. [NC₈H₅(CH₃)]₂[NC₈H₆(CH₃)]Al[C₂H₅] was identified by proton NMR. ¹H NMR (C₆D₆): δ 0.30(d), 0.86 (q), 1.29 (t), 2.38, (s), 2.4 (s), 2.5(sh), 6.6 (m), 7-8 (m).

The experiment was repeated with deuterated 3-methylindole(D). In this test run, the acidic H was approximately 50 to 80% deuterated. The resulting product revealed a loss of the peak intensity at 2.5. Furthermore, the doublet at 0.30 ppm resulted in a multiplet due to a deuterium neighbor.

Polymerizations

Polymerizations were performed in a glass-lined 20-mL autoclave reactor equipped with a mechanical stirrer, an external heater for temperature control, a septum inlet and a regulated supply of dry nitrogen and ethylene in an inert atmosphere (Nitrogen) glove box. The reactor was dried and degassed thoroughly at 115° C. The diluent and comonomer were added at room temperature and atmospheric pressure. The reactor was then brought to process pressure and charged with ethylene while stirring at 800 RPM. The activator and catalyst were added via syringe with the reactor at process conditions. The polymerization was continued while maintaining the reaction vessel within 3° C. of the target process temperature and 5 psig of target process pressure (by automatic addition of ethylene on demand) until a fixed uptake of ethylene was noted (corresponding to calculated 0.15 g polymer) or until a maximum reaction time of 20 minutes had passed. The reaction was stopped by pressurizing the reactor to 30 psig above the target process pressure with a gas mixture composed of 5 mol % oxygen in argon. The polymer was recovered by vacuum centrifugation of the reaction mixture. Bulk polymerization activity was calculated by dividing the yield of polymer by the total weight of the catalyst charge by the time in hours and by the absolute monomer pressure in atmospheres. The specific polymerization activity was calculated by dividing the yield of polymer by the total number of μmoles of transition metal contained in the catalyst charge by the time in hours.

Example 7

The reaction of triethylaluminum and 4,5,6,7-tetrafluoroindole was allowed to take place for six hours at room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with the aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. Polymerizations were then carried out. See Table 5. The solution was then aged for 24 hours, and the polymerization study was repeated. See Table 6.

The activity numbers in Tables 7 and 8 illustrate the large difference in polymerization activity between day 1 and 2. Not wishing to be bound by theory, the activity difference may be related to the slow activation rate between catalyst and activator and/or the slow formation of a reactive 4,5,6,7-tetrafluoroindolyl aluminum species at room temperature.

TABLE 7 Day 1: Polymerization of (1,3-MeBuCp)₂Zr—Me₂/Et2Al(4,5,6,7- tetrafluoroindolyl) (4,5,6,7-tetrafluoroindoleH). Comonomer Average Average Average Activity Row μmol. Zr Incorporation Mw Mn PDI Yield (g/μmol * hr) A 0.05 0.000 0.00 A 0.05 0.000 0.01 A 0.05 0.000 0.00 A 0.05 0.000 0.00 A 0.05 0.000 0.00 A 0.05 0.001 0.03 average 0.000 0.00 stddev 0.001 0.02 B 0.07 0.006 0.12 B 0.07 0.007 0.14 B 0.07 0.004 0.08 B 0.07 0.006 0.13 B 0.07 0.008 0.18 B 0.07 0.009 0.19 average 0.008 0.17 stddev 0.001 0.03 C 0.092 4.1 213426 124328 1.72 0.018 0.30 C 0.092 0.011 0.18 C 0.092 3.7 226262 133451 1.70 0.024 0.39 C 0.092 3.7 212638 125764 1.69 0.020 0.33 C 0.092 3.2 227958 138590 1.64 0.031 0.50 C 0.092 3.5 234483 140536 1.67 0.037 0.60 average 3 225026 134963 1.67 0.029 0.48 stddev 0 11214 8026 0.02 0.009 0.14 D 0.11 3.7 227161 136889 1.66 0.039 0.53 D 0.11 4.0 223867 132269 1.69 0.041 0.56 D 0.11 0.014 0.19 D 0.11 0.012 0.71 D 0.11 4.2 217413 130460 1.67 0.040 0.70 D 0.11 3.3 234065 138588 1.69 0.045 0.72 average 4 225739 134524 1.68 0.032 0.71 stddev 1 11774 5747 0.02 0.018 0.01 E 0.13 4.1 203694 122739 1.66 0.049 0.57 E 0.13 3.1 212643 126291 1.68 0.048 0.67 E 0.13 3.9 187767 113237 1.66 0.047 0.73 E 0.13 3.5 209049 121665 1.72 0.046 0.69 E 0.13 3.8 195957 117215 1.67 0.042 0.60 E 0.13 3.6 187573 110766 1.69 0.041 0.68 average 4 197526 116549 1.69 0.043 0.65 stddev 0 10824 5480 0.02 0.002 0.05 F 0.16 3.6 172873 104361 1.66 0.048 0.60 F 0.16 3.7 166283 99917.3 1.66 0.049 0.71 F 0.16 3.5 162240 99475.9 1.63 0.046 0.62

TABLE 8 Day 2: Polymerization of (1,3-MeBuCp)₂Zr—Me₂/Et2Al(4,5,6,7- tetrafluoroindolyl) (4,5,6,7-tetrafluoroindoleH). Actual □mol. Comonomer Average Average Average Quench Activity Zr Column Incorporation Mw Mn PDI Time Yield (g/μmol * hr) 0.05 1 2400.86 0.0106 0.32 0.05 2 2400.91 0.0144 0.43 0.05 3 2.98 185203 116321 1.59 2400.64 0.0212 0.64 0.05 4 2400.82 0.0058 0.17 0.05 5 5.03 182686 110824 1.65 2402.13 0.0155 0.46 0.05 6 4.01 175204 109579 1.60 2400.39 0.0153 0.46 average 4.52 178945 110202 1.62 2401.11 0.01 0.37 stddev 0.72 5291 881 0.04 0.91 0.01 0.17 0.07 1 5.97 152771 99558.1 1.53 600.59 0.0465 3.98 0.07 2 6.05 156945 103812 1.51 802.89 0.0420 2.69 0.07 3 6.15 141375 95382.2 1.48 646.33 0.0468 3.72 0.07 4 17.53 187405 120370 1.56 2058.99 0.0442 1.10 0.07 5 9.73 155668 104313 1.49 1389.22 0.0432 1.60 0.07 6 10.09 152454 103467 1.47 782.48 0.0427 2.81 average 12.45 165176 109383 1.51 1410.23 0.04 1.84 stddev 4.40 19318 9524 0.04 638.51 0.00 0.88 0.09 1 6.44 116408 79221.8 1.47 300.43 0.0514 6.69 0.09 2 7.12 124983 84600.4 1.48 223.94 0.0592 10.34 0.09 3 8.64 110404 75603.7 1.46 214.84 0.0578 10.53 0.09 4 18.65 121221 82913.3 1.46 243.87 0.0508 8.15 0.09 5 15.30 111898 75233.7 1.49 211.26 0.0512 9.48 0.09 6 9.07 113080 77885.9 1.45 186.62 0.0573 12.01 average 14.34 115400 78678 1.47 213.92 0.05 9.88 stddev 4.86 5076 3901 0.02 28.72 0.00 1.96 0.11 1 15.31 98977 65982.1 1.50 140.54 0.0705 16.42 0.11 2 17.88 103924 70978.8 1.46 144.4 0.0663 15.03 0.11 3 20.94 99984 67180.2 1.49 149.08 0.0694 15.24 0.11 4 16.59 96563 66162.7 1.46 128.68 0.0634 16.12 0.11 5 16.72 91384 61852.6 1.48 138 0.0636 15.08 0.11 6 25.33 95370 62787.2 1.52 115.52 0.0794 22.49 average 19.55 94439 63601 1.49 127.40 0.07 17.90 stddev 5.01 2712 2267 0.03 11.29 0.01 4.01 0.13 1 22.45 77789 50666.4 1.54 106.95 0.0802 20.77 0.13 2 31.48 75689 49686 1.52 94.69 0.0862 25.21 0.13 3 8.86 118278 78050.5 1.52 286.24 0.0471 4.56 0.13 4 14.25 92011 61865.6 1.49 120.66 0.0734 16.85 0.13 5 15.55 80492 53593.6 1.50 101.95 0.0692 18.80 0.13 6 18.66 83305 54841.5 1.52 107.34 0.0792 20.43 average 16.15 85269 56767 1.50 109.98 0.07 18.69 stddev 2.27 6005 4459 0.02 9.63 0.01 1.80 0.16 1 18.61 81009 53462.1 1.52 91.49 0.0817 20.09 0.16 2 17.71 72314 45790.3 1.58 92.88 0.0890 21.56 0.16 3 0.16 4 7.06 72262 46419.1 1.56 89.18 0.0783 19.75 0.16 5 6.82 67200 42625.8 1.58 92.8 0.0845 20.49 0.16 6 5.49 68634 44327.6 1.55 87.07 0.0833 21.53 average 6.46 69365 44457 1.56 89.68 0.08 20.59 stddev 0.85 2609 1900 0.01 2.90 0.00 0.89

Example 8

The reaction of triethylaluminum and two equivalents of 4,5,6,7-tertrafluoroindole was allowed to take place for three hours at room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with the aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. The solution was then aged for 24 hours, and the polymerization study was repeated.

Example 9

The reaction of triethylaluminum and two equivalents of 2-methylindole was allowed to take place for three hours at room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with the aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. The solution was then aged for 24 hours, and the polymerization study was repeated.

Example 10

The reaction of triethylaluminum and two equivalents of indole was allowed to take place for three hours at room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with the aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. The solution was then aged for 24 hours, and the polymerization study was repeated.

Example 11

The reaction of triethylaluminum and two equivalents of 5-bromoindole was allowed to take place for three hours at room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with the aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. The solution was then aged for 24 hours, and the polymerization study was repeated

Example 12

The reaction of triethylaluminum and two equivalents of 5-chloroindole was allowed to take place for three hours at room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with the aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. The solution was then aged for 24 hours, and the polymerization study was repeated.

For Examples 8-12, Table 9 shows the results of the polymerization after Day 1 and Table 10 shows the results of the polymerization after Day 2.

TABLE 9 Day 1. Actual Activity Aluminum Catalyst Comonomer Average Average Average Quench (g · Pol/μmol. “Activator” Micromoles Incorporation Mw Mn PDI Time Yield Cat · hr) tetrafluoroindolyl- 0.0125 2400 0.000 0.0000 Al- 0.0286 2403 0.000 0.0000 0.0446 2400 0.000 0.0000 0.0607 2401 0.001 0.0148 0.0768 2401 0.000 0.0078 0.0929 2402 0.002 0.0242 0.11 2401 0.003 0.0382 0.125 2400 0.005 0.0588 (2- 0.0125 2401 0.000 0.0000 Meindolyl) 0.0286 2400 0.000 0.0000 2AlEt2 0.0446 2402 0.000 0.0000 0.0607 2401 0.000 0.0000 0.0768 2400 0.000 0.0000 0.0929 2401 0.000 0.0000 0.11 2401 0.000 0.0000 0.125 2400 0.000 0.0000 indolyl-Al- 0.0125 2401 0.000 0.0000 0.0286 850 0.000 0.0000 0.0446 2400 0.001 0.0168 0.0607 2400 0.000 0.0000 0.0768 2400 0.000 0.0000 0.0929 2401 0.000 0.0000 0.11 2401 0.000 0.0000 0.125 2400 0.000 0.0000 5- 0.0125 2400 0.000 0.0000 bromoindolyl- 0.0286 2401 0.000 0.0000 Al 0.0446 2401 0.000 0.0000 0.0607 2401 0.000 0.0000 0.0768 2401 0.002 0.0332 0.0929 2401 0.014 0.2260 0.11 3.36 95067 60294 1.58 2400 0.035 0.4717 0.125 3.84 97849 60789 1.61 1420 0.044 0.8967 5- 5 1890 0.000 0.0000 choroindolyl- 5 2401 0.000 0.0000 Al 5 1471 0.000 0.0000 5 2401 0.003 0.0008 5 2401 0.008 0.0024 5 4.21 85418 47556 1.80 2400 0.032 0.0094 5 3.88 86901 50515 1.72 1144 0.039 0.0247 5 4.00 82552 48173 1.71 940 0.043 0.0330

TABLE 10 Day 2. Actual Activity Aluminum Comonomer Average Average Average Quench Catalyst (g · Pol./μmol. “Activator” Incorporation Mw Mn PDI Time Yield Micromoles Cat · hr) Tetrafluoroindolyl- 2401 0 0.013 0.0000 Al 2401 0.0015 0.029 0.0787 2401 0.0121 0.045 0.4063 8.78 135684 59452 2.28 2401 0.0289 0.061 0.7136 10.57 142433 89444 1.59 231 0.0475 0.077 9.6506 3.90 121712 78227 1.56 155 0.0537 0.093 13.4109 4.72 106841 67425 1.58 109 0.0672 0.109 20.3101 4.73 93558 57790 1.62 102 0.0745 0.125 21.0065 2- 2401 0 0.013 0.0000 Meindolyl- 2400 0 0.029 0.0000 Al 2400 0 0.045 0.0000 2400 0 0.061 0.0000 2402 0 0.077 0.0000 2401 0 0.093 0.0000 2400 0 0.109 0.0000 2401 0 0.125 0.0000 indolyl-Al 2401 0 0.013 0.0000 2401 0 0.029 0.0000 2401 0 0.045 0.0000 2400 0.0021 0.061 0.0519 2400 0.0022 0.077 0.0430 2401 0.0058 0.093 0.0937 2401 0.0061 0.109 0.0840 2400 0.0087 0.125 0.1044 5- 2401 0 0.013 0.0000 bromoindolyl- 2401 0 0.029 0.0000 Al 2401 0.0036 0.045 0.1209 2401 0.008 0.061 0.1975 3.32 173216 80724 2.15 2401 0.0154 0.077 0.3007 3.05 163787 78365 2.09 2401 0.0226 0.093 0.3649 3.47 135806 65253 2.08 2401 0.0303 0.109 0.4171 3.52 139184 68634 2.03 2400 0.0346 0.125 0.4152 5- 1533 0 0.013 0.0000 chloroindolyl- 2401 0.0042 0.029 0.2204 Al 1097 0.0096 0.045 0.7058 15.07 145258 72788 2.00 971 0.039 0.061 2.3819 3.60 158883 75427 2.11 516 0.0395 0.077 3.5867 3.16 142940 67343 2.12 396 0.0454 0.093 4.4398 3.18 130638 61686 2.12 285 0.0492 0.109 5.6971 3.14 130193 60937 2.14 262 0.0534 0.125 5.8751

Example 13

The reaction of triethylaluminum and three equivalents of 4,5,6,7-tetrafluoroindole was allowed to take place overnight room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with the aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. Polymerizations were then carried out, Table 11.

Example 14

The reaction of triethylaluminum and three equivalents of indole was allowed to take place overnight room temperature (1,3-MeBuCp)₂Zr-Me₂ was reacted with each aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. Polymerizations were then carried out.

Example 15

The reaction of triethylaluminum and three equivalents of 5-bromoindole was allowed to take place overnight room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with each aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. Polymerizations were then carried out.

Example 16

The reaction of triethylaluminum and three equivalents of 5-chloroindole was allowed to take place overnight room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with each aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. Polymerizations were then carried out.

Example 17

The reaction of triethylaluminum and three equivalents of 3-methylindole was allowed to take place overnight room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with each aluminum complex in a ratio of 1:3. Ethylene-octene copolymerizations were then performed at 100° C. Polymerizations were then carried out.

For Examples 13-17, Table 11 shows the results of the polymerization after Day 1 and Table 12 shows the results of the polymerization after Day 2.

TABLE 11 Actual Activity Aluminum Comonomer Average Average Average Quench Catalyst (g · Pol./μmol. “Activator” Incorporation Mw Mn PDI Time Yield Micromoles Cat · hr) Tetrafluoroindolyl- 2400.35 0 0.013 0.000 Al 2400.79 0.0031 0.029 0.163 3.94 174462 103575 1.6844 2400.18 0.0197 0.045 0.662 3.68 159600 101757 1.5684 1066.9 0.0457 0.061 2.540 3.71 134641 89973 1.4965 270.52 0.0592 0.077 10.260 4.26 112771 75710 1.4895 188.09 0.0641 0.093 13.212 4.09 99824 66081 1.5106 164.08 0.0741 0.109 14.925 3.9 89127 58198 1.5314 129.13 0.0811 0.125 18.088 indolyl-Al 2400.24 0 0.013 0.000 2400.67 0 0.029 0.000 2401.55 0 0.045 0.000 2400.33 0 0.061 0.000 2400.35 0.0008 0.077 0.016 2400.67 0.0014 0.093 0.023 2401.36 0.002 0.109 0.028 2400.52 0.0025 0.125 0.030 5- 2400.8 0 0.013 0.000 bromoindolyl- 2400.78 0.0036 0.029 0.189 Al 3.78 104300 58848 1.77 2400.18 0.0281 0.045 0.944 2.89 110725 65414 1.69 1466.38 0.0427 0.061 1.727 3.04 110209 65311 1.68 971.21 0.0448 0.077 2.163 690.67 0.0045 0.093 0.253 3.26 90126 54994 1.63 592.03 0.0462 0.109 2.579 3.05 84229 51483 1.63 518.4 0.0487 0.125 2.706 5- 2241.81 0 0.013 0.000 chloroindolyl- 2401.09 0.0008 0.029 0.042 Al 1414.06 0.0045 0.045 0.257 2.85 100366 64405 1.55 2400.8 0.0318 0.061 0.785 2.91 106266 69026 1.53 1596.36 0.0399 0.077 1.172 3.08 98444 64280 1.53 1193.77 0.042 0.093 1.364 3.14 85063 55874 1.52 881.81 0.044 0.109 1.649 3.19 88189 57926 1.52 734.19 0.0451 0.125 1.769 3- 2400.7 0 0.013 0.0000 Meindolyl2 2400.6 0.0001 0.03 0.0052 AlEt(H-3- 2400.83 0.0007 0.04 0.0235 Methyindoyl) 2400.54 0.0004 0.06 0.0099 2400.54 0.0019 0.08 0.0371 2400.14 0.002 0.09 0.0323 2400.27 0.0029 0.11 0.0399 2400.35 0.0037 0.13 0.0444

Example 18

The reaction of triethylaluminum and four equivalents of 4,5,6,7-tetrafluoroindole was allowed to take place overnight room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with each aluminum complex in a ratio of 1:3. Ethylene octene copolymerizations were then performed at 100° C. Polymerizations were then carried out.

Example 19

The reaction of triethylaluminum and four equivalents of indole was allowed to take place overnight room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with each aluminum complex in a ratio of 1:3. Ethylene octene copolymerizations were then performed at 100° C. Polymerizations were then carried out.

Example 20

The reaction of triethylaluminum and four equivalents of 5-bromoindole was allowed to take place overnight room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with each aluminum complex in a ratio of 1:3. Ethylene octene copolymerizations were then performed at 100° C. Polymerizations were then carried out.

Example 21

The reaction of triethylaluminum and four equivalents of 5-chloroindole was allowed to take place overnight room temperature. (1,3-MeBuCp)₂Zr-Me₂ was reacted with each aluminum complex in a ratio of 1:3. Ethylene octene copolymerizations were then performed at 100° C. Polymerizations were then carried out.

For Examples 18-21, Table 12 shows the results of the polymerization.

TABLE 12 Actual Activity Aluminum Comonomer Average Average Average Quench Catalyst (g · Pol./μmol. “Activator” Incorporation Mw Mn PDI Time Yield Micromoles Cat · hr) Tetrafluoroindolyl- 2400.9 0 0.013 0.000 Al 2401.1 0.0015 0.029 0.079 2400.5 0.0111 0.045 0.373 4.07 185606 110905 1.67 2400.0 0.0413 0.061 1.020 4.33 141236 84795 1.67 354.2 0.0542 0.077 7.174 3.82 115109 72882 1.58 147.5 0.0627 0.093 16.481 4.14 102135 68055 1.50 136.1 0.0718 0.109 17.438 4.33 103285 66836 1.55 109.5 0.081 0.125 21.296 indolyl-Al 2400.2 0 0.013 0.000 2401.1 0 0.029 0.000 2400.7 0 0.045 0.000 2400.0 0 0.061 0.000 2400.8 0 0.077 0.000 2401.3 0 0.093 0.000 2400.8 0 0.109 0.000 2400.2 0 0.125 0.000 5- 2401.0 0 0.013 0.000 bromoindolyl- 2401.2 0 0.029 0.000 Al 2400.2 0.0012 0.045 0.040 2400.8 0.0141 0.061 0.348 2.64 98688 63321 1.56 2400.7 0.0274 0.077 0.535 2.84 99622 66442 1.50 1421.8 0.0408 0.093 1.113 3.22 86623 57763 1.50 1022.1 0.0444 0.109 1.436 2.96 89849 59196 1.52 821.0 0.044 0.125 1.543 5- 1921.0 −0.0006 0.013 0.000 chloroindolyl- 2401.1 −0.0007 0.029 0.000 Al 1642.1 0.0002 0.045 0.010 2401.9 0.0144 0.061 0.355 2.73 87550 57859 1.51 2401.1 0.0303 0.077 0.592 3.64 91305 61573 1.48 1488.3 0.0388 0.093 1.011 3.12 81885 54488 1.50 1022.7 0.0416 0.109 1.344 3.24 82966 55954 1.48 792.4 0.0411 0.125 1.494

In the following non-limiting examples 22-25: carbazole was purchased from Aldrich and used as received; anhydrous toluene and pentane were purchased from Aldrich and dried overnight over a sodium potassium alloy; and (1,3-MeBuCp)₂Zr-Me₂, 20 wt % solution in toluene was purchased from Norquay Single-Site Catalysts and used as received.

Example 22

Carbazole (0.5 grams) was combined with triethylaluminum (0.114 grams) in toluene (40 mls). Ethane evolution from the solution was observed. The solution was left overnight at 100 C with a slow nitrogen purge. Yellow crystals grew from the solution.

Single crystals of [NC₁₂H₈]₄Al(H) were subjected to X-rays by Victor Day at Crystalytics, located in Lincoln, Nebr. The X-ray structure determination revealed a neutral four-coordinate aluminum center. An ORTEP of the structure is displayed in FIG. 2 a and a ball and stick perspective drawing of the solid-state structure is shown in FIG. 2 b. Atomic Coordinates for Nonhydrogen Atoms are listed in Table 13, and Anisotropic Thermal Parameters are listed in Table 14. Atomic Coordinates for Hydrogen Atoms are listed in Table 15. Selected bond lengths and bond angles are listed in Tables 16 and 17, respectively. Torsion angles are listed in Table 18.

TABLE 13 Atomic Coordinates for Nonhydrogen Atoms in Crystalline [NC₁₂H₈]₃Al[HNC₁₂H₈].C₆H₅CH₃ ^(a) Atom Fraction Coordinates Equivalent Isotropic Thermal Type^(b) 10⁴x 10⁴y 10⁴z Parameter, U, {acute over (Å)}² × 10^(3c) Al 2734(2) 2086(1) 1059(1)  51(1) N₁ 2047(4) 1431(3)  777(2)  51(2) N₂ 3378(4) 2628(3)  638(2)  53(2) N3 3366(4) 1651(3) 1540(2)  58(2) N4 1951(4) 2797(3) 1352(2)  45(2) C₁ 2304(5)  988(4)  403(3)  45(2) C₂ 3016(5) 1055(4)  79(2)  49(2)^(d) C₃ 3142(5)  558(4) −280(3)  60(2)^(d) C₄ 2581(5)   0(4) −307(3)  64(2)^(d) C₅ 1897(5)  −83(4)  14(3)  64(2)^(d) C₆ 1765(5)  413(4)  374(3)  48(2) C₇ 1121(5)  478(4)  752(3)  49(2) C₈  432(5)  83(4)  902(3)  65(2)^(d) C₉  −79(5)  283(4) 1287(3)  62(2)^(d) C₁₀  95(5)  893(4) 1523(3)  60(2)^(d) C₁₁  787(5) 1306(4) 1381(3)  59(2)^(d) C₁₂ 1304(5) 1110(4)  986(3)  45(2) C₂₁ 3167(5) 2794(3)  152(3)  48(2) C₂₂ 2396(5) 2646(4)  −96(3)  57(2)^(d) C₂₃ 2328(5) 2898(4) −571(3)  67(2)^(d) C₂₄ 3022(5) 3257(4) −780(3)  65(2)^(d) C₂₅ 3784(5) 3379(4) −547(3)  62(2)^(d) C₂₆ 3861(6) 3152(4)  −65(3)  53(2) C₂₇ 4528(5) 3232(4)  294(3)  54(2) C₂₈ 5352(5) 3523(4)  297(3)  64(2)^(d) C₂₉ 5848(5) 3533(4)  709(3)  69(3)^(d) C₃₀ 5530(5) 3250(4) 1136(3)  65(2)^(d) C₃₁ 4712(5) 2943(3) 1149(3)  55(2)^(d) C₃₂ 4221(5) 2918(4)  731(3)  53(2) C₄₁ 4131(5) 1265(40 1436(3)  52(2) C₄₂ 4681(5) 1289(4) 1027(3)  67(3)^(d) C₄₃ 5410(5)  870(4) 1009(3)  66(2)^(d) C₄₄ 5588(5)  424(4) 1400(3)  70(2)^(d) C₄₅ 5061(5)  386(4) 1797(3)  75(3)^(d) C₄₆ 4319(5)  793(4) 1818(3)  59(2) C₄₇ 3645(6)  880(4) 2167(3)  56(2) C₄₈ 3459(5)  554(4) 2608(3)  65(2)^(d) C₄₉ 2728(5)  756(4) 2862(3)  79(3)^(d) C₅₀ 2182(5) 1279(4) 2711(3)  75(3)^(d) C₅₁ 2362(5) 1612(4) 2265(3)  68(2)^(d) C₅₂ 3092(5) 1406(4) 1994(3)  57(2) C₆₁ 2450(5) 3371(4) 1571(3)  48(2) C₆₂ 3028(5) 3339(4) 1954(3)  55(2) C₆₃ 3393(5) 3954(5) 2103(3)  62(2) C₆₄ 3181(6) 4569(4) 1887(3)  68(3) C₆₅ 2607(5) 4595(4) 1506(3)  59(2) C₆₆ 2244(5) 3978(4) 1342(3)  48(2) C₆₇ 1583(5) 3849(4)  969(3)  46(2) C₆₈ 1134(6) 4262(4)  655(3)  59(2) C₆₉  481(6) 3984(4)  361(3)  66(3) C₇₀  293(5) 3280(4)  388(3)  58(2) C₇₁  740(5) 2864(4)  708(3)  52(2) C₇₂ 1402(5) 3146(4)  988(3)  43(2) Toluene Solvent Molecule of Crystallization C_(1S) 4404(10) 3102(8) 3155(4) 104(4) C_(2S) 4363(8) 2515(6) 2896(5)  99(4) C_(3S) 5001(11) 2388(6) 2554(5) 101(4) C_(4S) 5656(9) 2844(10) 2482(5) 127(5) C_(5S) 5712(11) 3456(11) 2746(7) 151(8) C_(6S) 5062(13) 3546(7) 3081(6) 134(7) C_(7S) 3634(9) 3235(6) 3518(4) 172(5) ^(a)The numbers in parentheses are the estimated standard deviations in the last significant digit. ^(b)Atoms are labeled in agreement with FIG. 2A. ^(c)This is one-third of the trace of the orthogonalized U_(ij) tensor. ^(d)This atom was included in the structural model with an isotropic thermal parameter and this is its final refined value.

TABLE 14 Anisotropic Thermal Parameters for Nonhydrogen Atoms in Crystalline [NC₁₂H₈]₃Al[HNC₁₂H₈].C₆H₅CH₃ ^(a,b) Atom Anisotropic Thermal Parameters ({acute over (Å)}² × 10³) Type^(c) U₁₁ U₂₂ U₃₃ U₂₃ U₁₃ U₁₂ Al 59(2) 41(1) 53(2) 0(1) 4(1) 5(1) N₁ 67(5) 32(4) 53(4) −5(4)   10(4)  −3(4)   N₂ 63(5) 44(4) 52(5) 5(4) 4(4) −1(4)   N₃ 55(5) 53(4) 65(5) 9(4) −4(4)   16(4)  N₄ 52(5) 34(4) 47(5) 1(4) −3(4)   0(4) C₁ 50(5) 27(4) 57(6) 5(4) 0(4) 5(4) C₆ 64(6) 26(5) 55(6) 6(4) 9(5) 8(4) C₇ 55(6) 41(5) 52(6) 13(5)  12(5)  0(4) C₁₂ 58(6) 25(5) 52(6) 3(4) 3(5) 5(4) C₂₁ 62(6) 28(5) 55(6) 4(4) 10(5) 6(4) C₂₆ 65(6) 34(5) 60(7) −3(5)   15(5)  4(4) C₂₇ 54(6) 39(5) 70(7) −2(5)   6(5) 0(4) C₃₂ 67(7) 27(5) 64(7) 2(5) 4(5) 6(4) C₄₁ 62(6) 34(5) 58(6) 3(5) −18(5)    2(4) C₄₆ 60(6) 56(6) 61(7) −3(5)   −3(5)   −7(5)   C₄₇ 76(7) 42(6) 51(6) 5(5) −14(5)    −14(5)    C₅₂ 71(7) 52(6) 49(6) 4(5) 5(5) −9(5)   C₆₁ 66(6) 29(5) 49(6) 7(4) 1(5) 2(4) C₆₂ 61(6) 53(6) 50(6) 7(5) −4(5)   0(5) C₆₃ 64(6) 52(6) 69(7) −12(6)    −6(5)   −12(5)    C₆₄ 88(7) 35(6) 82(7) −7(6)   1(6) −6(5)   C₆₅ 69(7) 51(6) 56(6) 9(5) −3(5)   −5(5)   C₆₆ 58(6) 35(5) 51(6) −2(5)   12(5)  −7(5)   C₆₇ 51(6) 32(5) 54(6) 7(5) 10(5)  5(4) C₆₈ 74(7) 43(6) 60(6) 15(5)  9(5) −4(5)   C₆₉ 73(7) 62(7) 62(7) 12(5)  −7(5)   22(5)  C₇₀ 62(6) 50(6) 62(6) 9(5) 2(5) 10(5)  C₇₁ 61(6) 42(5) 53(6) 1(5) 0(5) 0(5) C₇₂ 55(6) 33(5) 41(5) 2(4) 9(4) 9(4) Toluene Solvent Molecule of Crystallization C_(1S) 168(14) 65(9) 79(9) −11(8)    −34(8)    34(9)  C_(2S) 121(11) 60(9) 116(11) 13(8)  −46(9)    6(7) C_(3S) 125(12) 72(9) 106(11) −17(8)    −57(9)    10(9)  C_(4S) 106(12) 138(13) 137(13) 39(12) −52(9)    15(11) C_(5S) 131(16) 116(15) 210(20) 56(15) −114(14)    −20(14)   C_(6S) 200(20) 42(8) 162(17) 31(10) −125(14)    −35(12)   C_(7S) 257(17) 140(11) 119(11) 18(10) −38(12)   35(11) ^(a)The numbers in parentheses are the estimated standard deviations in the last significant digit. ^(b)The form of the anisotropic thermal parameter is: exp[−2_(Π) ²(U₁₁h²a*² + U₂₂k²b*² + U₃₃l²c*² + 2U₁₂hka*b* + 2U₁₃hla*c* + 2U₂₃klb*c*)]. ^(c)Atoms are labeled in agreement with FIG. 2A.

TABLE 15 Atomic Coordinates for Hydrogen Atoms in Crystalline [NC₁₂H₈]₃Al[HNC₁₂H₈].C₆H₅CH₃ ^(a) Atom Fractional Coordinates Type^(b) 10⁴x 10⁴y 10⁴z H_(4N) ^(c) 1550(30) 2540(30) 1554(18) H₂ 3406 1432 105 H₃ 3609 604 −504 H₄ 2672 −332 −552 H₅ 1521 −469 −8 H₈ 306 −333 738 H₉ −552 3 1392 H₁₀ −265 1031 1787 H₁₁ 909 1718 1549 H₂₂ 1939 2387 48 H₂₃ 1806 2823 −751 H₂₄ 2954 3423 −1101 H₂₅ 4253 3610 −703 H₂₈ 5579 3719 9 H₂₉ 6415 3734 704 H₃₀ 5877 3268 1421 H₃₁ 4494 2752 1441 H₄₂ 4553 1589 766 H₄₃ 5790 881 737 H₄₄ 6093 142 1384 H₄₅ 5200 85 2055 H₄₈ 3830 203 2728 H₄₉ 2592 526 3155 H₅₀ 1694 1413 2902 H₅₁ 1993 1969 2152 H₆₂ 3168 2919 2108 H₆₃ 3803 3952 2362 H₆₄ 3437 4979 2004 H₆₅ 2460 5017 1357 H₆₈ 1267 4735 637 H₆₉ 165 4268 144 H₇₀ −145 3090 184 H₇₁ 597 2393 736 Toluene Solvent Molecule of Crystallization H_(2S) 3903 2197 2949 H_(3S) 4981 1980 2368 H_(4S) 6091 2748 2246 H_(5S) 6165 3781 2696 H_(6S) 5076 3948 3273 H_(7Sa) 3242 2838 3523 H_(7Sb) 3305 3640 3416 H_(7Sc) 3873 3309 3843 ^(a)The carbazolyl amine proton (H_(4N)) was located from a difference Fourier syntheses and refined as an independent isotropic atom. The remaining hydrogen atoms were included in the structural model as fixed atoms (using idealized sp² - or sp³ - hybridized geometry and C—H bond lengths of 0.95-0.98 {acute over (Å)}) “riding” on their respective carbons. The isotropic thermal parameter of H_(4N) refined to a final U_(iso) value of 0.06(2) {acute over (Å)}2. # The isotropic thermal parameters of all remaining hydrogen atoms were fixed at values 1.2 (nonmethyl) or 1.5 (methyl) times the equivalent isotropic thermal parameter of the carbon atom to which they are covalently bonded. ^(b)Hydrogen atoms bonded to carbon are labeled with the same numerical and literal subscript(s) as their carbon atoms and carry an additional literal subscript (a, b or c) where necessary to distinguish between hydrogens bonded to the same carbon. ^(c)The numbers in parentheses are the estimated standard deviations in the last significant digit.

TABLE 16 Bond Lengths in Crystalline [NC₁₂H₈]₃Al[HNC₁₂H₈].C₆H₅CH₃ ^(a) Type^(b) Length, {acute over (Å)} Type^(b) Length, {acute over (Å)} Al—N₁ 1.831(6) N₁—C₁ 1.406(8) Al—N₂ 1.856(6) N₁—C₁₂ 1.419(8) Al—N₃ 1.852(6) N₂—C₂₁ 1.418(8) N₂—C₃₂ 1.429(8) Al—N₄ 2.006(6) N₃—C₄₁ 1.418(8) N₃—C₅₂ 1.407(8) N₄—C₆₁ 1.485(8) N₄—C₇₂ 1.476(8) N₄—H_(4N)  0.97(2) C₁-C₂ 1.413(9) C₄₁-C₄₂  1.411(10) C₁-C₆ 1.397(9) C₄₁-C₄₆ 1.432(9) C₂-C₃ 1.403(8) C₄₂-C₄₃ 1.384(9) C₃-C₄ 1.390(9) C₄₃-C₄₄ 1.413(9) C₄-C₅ 1.380(9) C₄₄-C₄₅ 1.363(9) C₅-C₆ 1.407(9) C₄₅-C₄₆ 1.386(9) C₆-C₇ 1.439(9) C₄₆-C₄₇  1.420(10) C₇-C₈ 1.369(9) C₄₇-C₄₈ 1.406(9) C₇-C₁₂ 1.423(9) C₄₇-C₅₂ 1.414.(9) C₈-C₉ 1.379(8) C₄₈-C₄₉ 1.376(9) C₉-C₁₀ 1.388(8) C₄₉-C₅₀ 1.386(9) C₁₀-C₁₁ 1.386(8) C₅₀-C₅₁ 1.421(9) C₁₁-C₁₂ 1.401(9) C₅₁-C₅₂ 1.401(9) C₂₁-C₂₂ 1.392(9) C₆₁-C₆₂ 1.380(9) C₂₁-C₂₆ 1.405(9) C₆₁-C₆₆ 1.382(8) C₂₂-C₂₃ 1.407(9) C₆₂-C₆₃ 1.390(9) C₂₃-C₂₄ 1.395(9) C₆₃-C₆₄ 1.382.(9) C₂₄-C₂₅ 1.351(9) C₆₄-C₆₅ 1.372(9) C₂₅-C₂₆ 1.409(9) C₆₅-C₆₆ 1.404(9) C₂₆-C₂₇ 1.432(10) C₆₆-C₆₇ 1.463(9) C₂₇-C₂₈ 1.381(9) C₆₇-C₆₈ 1.372(9) C₂₇-C₃₂ 1.432(9) C₆₇-C₇₂ 1.405(8) C₂₈-C₂₉ 1.367(9) C₆₈-C₆₉ 1.396(9) C₂₉-C₃₀ 1.391(9) C₆₉-C₇₀ 1.411(9) C₃₀-C₃₁ 1.385(9) C₇₀-C₇₁ 1.384(9) C₃₁-C₃₂ 1.379(9) C₇₁-C₇₂ 1.386(9) Toluene Solvent Molecule of Crystallization C_(1S)-C_(2S) 1.356(13) C_(4S)-C_(5S) 1.405(17)  C_(1S)-C_(6S) 1.344(16) C_(5S)-C_(6S) 1.368(18)  C_(2S)-C_(3S) 1.379(13) C_(3S)-C_(4S) 1.355(14) C_(1S)-C_(7S) 1.567(15)  ^(a)The numbers in parentheses are the estimated standard deviations in the last significant digit. ^(b)Atoms are labeled in agreement with FIG. 2A.

TABLE 17 Bond Angles in Crystalline [NC₁₂H₈]₃Al[HNC₁₂H₈].C₆H₅CH₃ ^(a) Type^(b) Angle, (deg) Type^(b) Angle, (deg) N₁AlN₂ 115.9(3) C₁N₁Al 125.9(5) N₁AlN₃ 106.3(3) C₁₂N₁Al 126.5(5) N₁AlN₄ 108.5(3) C₁N₁C₁₂ 104.4(6) N₃AlN₂ 116.0(3) C₂₁N₂Al 127.2(6) N₂AlN₄  99.9(3) C₃₂N₂Al 126.2(6) N₃AlN₄ 109.8(3) C₂₁N₂C₃₂ 106.4(6) C₄₁N₃Al 121.8(6) C₆₁N₄Al 112.6(4) C₅₂N₃Al 130.0(6) C₇₂N₄Al 112.6(4) C₅₂N₃C₄₁ 104.1(6) C₇₂N₄C₆₁ 102.6(6) C₆₁N₄H_(4N)   119(4) AlN₄H_(4N)   105(4) C₇₂N₄H_(4N)   106(4) N₁C₁C₂ 128.5(7) C₄₂C₄₁N₃ 129.4(8) C₆C₁N₁ 112.0(6) N₃C₄₁C₄₆ 111.1(7) C₆C₁C₂ 119.4(7) C₄₂C₄₁C₄₆ 119.6(8) C₃C₂C₁ 119.3(7) C₄₃C₄₂C₄₁ 119.1(8) C₄C₃C₂ 120.0(7) C₄₂C₄₃C₄₄ 119.6(8) C₅C₄C₃ 121.6(8) C₄₅C₄₄C₄₃ 122.5(8) C₄C₅C₆ 118.8(7) C₄₄C₄₅C₄₆ 118.9(8) C₁C₆C₅ 120.9(7) C₄₅C₄₆C₄₁ 120.3(8) C₁C₆C₇ 106.8(7) C₄₇C₄₆C₄₁ 106.1(7) C₅C₆C₇ 132.3(8) C₄₅C₄₆C₄₇ 133.5(9) C₈C₇C₆ 133.8(8) C₄₈C₄₇C₄₆ 133.0(9) C₁₂C₇C₆ 105.8(6) C₅₂C₄₇C₄₆ 106.9(7) C₈C₇C₁₂ 120.3(7) C₄₈C₄₇C₅₂ 120.2(9) C₇C₈C₉ 120.5(8) C₄₉C₄₈C₄₇ 118.5(8) C₈C₉C₁₀ 120.0(8) C₄₈C₄₉C₅₀ 123.1(8) C₉C₁₀C₁₁ 121.0(8) C₄₉C₅₀C₅₁ 119.0(8) C₁₀C₁₁C₁₂ 119.4(8) C₅₂C₅₁C₅₀ 119.0(8) N₁C₁₂C₇ 110.9(6) N₃C₅₂C₄₇ 111.8(7) C₁₁C₁₂N₁ 130.2(7) C₅₁C₅₂N₃ 127.9(8) C₁₁C₁₂C₇ 118.8(7) C₅₁C₅₂C₄₇ 120.3(8) C₂₂C₂₁N₂ 127.7(7) C₆₂C₆₁N₄ 127.2(7) C₂₆C₂₁N₂ 110.4(7) C₆₆C₆₁N₄ 110.3(7) C₂₂C₂₁C₂₆ 121.9(8) C₆₂C₆₁C₆₆ 122.4(7) C₂₁C₂₂C₂₃ 116.8(7) C₆₁C₆₂C₆₃ 116.3(7) C₂₄C₂₃C₂₂ 120.4(8) C₆₄C₆₃C₆₂ 122.2(8) C₂₅C₂₄C₂₃ 123.1(8) C₆₅C₆₄C₆₃ 120.9(8) C₂₄C₂₅C₂₆ 117.7(8) C₆₄C₆₅C₆₆ 117.9(8) C₂₁C₂₆C₂₅ 120.0(8) C₆₁C₆₆C₆₅ 120.2(8) C₂₁C₂₆C₂₇ 107.0(7) C₆₁C₆₆C₆₇ 109.3(7) C₂₅C₂₆C₂₇ 132.9(8) C₆₅C₆₆C₆₇ 130.3(8) C₂₈C₂₇C₂₆ 134.1(9) C₆₈C₆₇C₆₆ 133.5(8) C₂₆C₂₇C₃₂ 107.8(7) C₇₂C₆₇C₆₆ 106.2(7) C₂₈C₂₇C₃₂ 118.1(8) C₆₈C₆₇C₇₂ 120.2(8) C₂₉C₂₈C₂₇ 120.9(8) C₆₇C₆₈C₆₉ 119.7(8) C₂₈C₂₉C₃₀ 120.6(8) C₆₈C₆₉C₇₀ 119.7(8) C₃₁C₃₀C₂₉ 120.5(8) C₇₁C₇₀C₆₉ 120.6(8) C₃₂C₃₁C₃₀ 118.9(8) C₇₀C₇₁C₇₂ 118.8(7) N₂C₃₂C₂₇ 108.3(7) C₆₇C₇₂N₄ 111.5(7) C₃₁C₃₂N₂ 130.8(8) C₇₁C₇₂N₄ 127.5(7) C₃₁C₃₂C₂₇ 120.8(8) C₇₁C₇₂C₆₇ 120.9(7) Toluene Solvent Molecule of Crystallization C_(6S)C_(1S)C_(2S)   120(1) C_(4S)C_(3S)C_(2S)   120(1) C_(2S)C_(1S)C_(7S)   116(2) C_(3S)C_(4S)C_(5S)   122(2) C_(6S)C_(1S)C_(7S)   123(2) C_(6S)C_(5S)C_(4S)   115(2) C_(1S)C_(2S)C_(3S)   119(1) C_(1S)C_(6S)C_(5S)   124(2) ^(a)The numbers in parentheses are the estimated standard deviations in the last significant digit. ^(b)Atoms are labeled in agreement with FIG. 2A.

TABLE 18 Torsion Angles in Crystalline [NC₁₂H₈]₃Al[HNC₁₂H₈].C₆H₅CH₃ ^(a) Type^(b) Angle, (deg) Type^(b) Angle, (deg) N₃—Al—N₁—C₁ −85.3(6) C₂₉-C₃₀-C₃₁-C₃₂ 0.4(11) N₂—Al—N₁—C₁ 45.3(6) C₃₀-C₃₁-C₃₂—N₂ 178.8(7) N₄—Al—N₁—C₁ 156.6(5) C₃₀-C₃₁-C₃₂-C₂₇ −3.0(10) N₃—Al—N₁—C₁₂ 71.3(6) C₂₁—N₂—C₃₂-C₃₁ 176.1(7) N₂—Al—N₁—C₁₂ −158.2(5) Al—N₂—C₃₂-C₃₁ −8.2(11) N₄—Al—N₁—C₁₂ −46.8(6) C₂₁—N₂—C₃₂-C₂₇ −2.3(7) N₁—Al—N₂—C₂₁ 27.4(6) Al—N₂—C₃₂-C₂₇ 173.4(5) N₃—Al—N₂—C₂₁ 153.2(5) C₂₈-C₂₇-C₃₂-C₃₁ 4.0(11) N₄—Al—N₂—C₂₁ −88.9(6) C₂₆-C₂₇-C₃₂-C₃₁ −177.1(6) N₁—Al—N₂—C₃₂ −147.5(5) C₂₈-C₂₇-C₃₂—N₂ −177.5(6) N₃—Al—N₂—C₃₂ −21.7(6) C₂₆-C₂₇-C₃₂—N₂ 1.5(8) N₄—Al—N₂—C₃₂ 96.2(6) C₅₂—N₃—C₄₁-C₄₂ 179.5(7) N₁—Al—N₃—C₅₂ −73.3(7) Al—N₃—C₄1-C₄₂ 20.1(10) N₂—Al—N₃—C₅₂ 156.2(6) C₅₂—N₃—C₄₁-C₄₆ 0.2(8) N₄—Al—N₃—C₅₂ 43.9(7) Al—N₃—C₄₁-C₄₆ −159.3(5) N₁—Al—N₃—C₄₁ 80.3(6) N₃—C₄₁-C₄₂-C₄₃ 178.5(7) N₂—Al—N₃—C₄₁ −50.2(6) C₄₆-C₄₁-C₄₂-C₄₃ −2.1(11) N₄—Al—N₃—C₄₁ −162.5(5) C₄₁-C₄₂-C₄₃-C₄₄ 0.3(11) N₁—Al—N₄—C₇₂ −61.9(6) C₄₂-C₄₃-C₄₄-C₄₅ 0.5(11) N₃—Al—N₄—C₇₂ −177.7(5) C₄₃-C₄₄-C₄₅-C₄₆ 0.7(12) N₂—Al—N₄—C₇₂ 59.9(5) C₄₄-C₄₅-C₄₆-C₄₇ −179.9(8) N₁—Al—N₄—C₆₁ −177.3(5) C₄₄-C₄₅-C₄₆-C₄₁ −2.5(11) N₃—Al—N₄—C₆₁ 66.8(5) C₄₂-C₄₁-C₄₆-C₄₅ 3.3(11) N₂—Al—N₄—C₆₁ −55.6(5) N₃—C₄₁-C₄₆-C₄₅ −177.3(7) C₁₂—N1—C₁-C₆ −0.6(8) C₄₂-C₄₁-C₄₆-C₄₇ −178.7(7) Al—N₁—C₁-C₆ 160.1(5) N₃—C₄₁-C₄₆-C₄₇ 0.8(8) C₁₂—N₁—C₁-C₂ −179.2(7) C₄₅-C₄₆-C₄₇-C₄₈ −4.4(16) Al—N₁—C₁-C₂ −18.5(10) C₄₁-C₄₆-C₄₇-C₄₈ 177.9(7) C₆-C₁-C₂-C₃ 3.2(10) C₄₅-C₄₆-C₄₇-C₅₂ 176.3(8) N₁—C₁-C₂-C₃ −178.2(6) C₄₁-C₄₆-C₄₇-C₅₂ −1.4(8) C₁-C₂-C₃-C₄ −1.6(10) C₅₂-C₄₇-C₄₈-C₄₉ 0.5(11) C₂-C₃-C₄-C₅ −0.2(11) C₄₆-C₄₇-C₄₈-C₄₉ −178.7(8) C₃-C₄-C₅-C₆ 0.3(11) C₄₇-C₄₈-C₄₉-C₅₀ −2.0(12) N₁—C₁-C₆-C₅ 178.1(6) C₄₈-C₄₉-C₅₀-C₅₁ 2.1(12) C₂-C₁-C₆-C₅ −3.1(10) C₄₉-C₅₀-C₅₁-C₅₂ −0.6(11) N₁—C₁-C₆-C₇ −0.3(8) C₅₀-C₅₁-C₅₂—N₃ 177.6(7) C₂-C₁-C₆-C₇ 178.5(6) C₅₀-C₅₁-C₅₂-C₄₇ −0.8(11) C₄-C₅-C₆-C₁ 1.3(10) C₄₁—N₃—C₅₂-C₅₁ −179.7(7) C₄-C₅-C₆-C₇ 179.3(7) Al—N₃—C₅₂-C₅₁ −22.6(12) C₁-C₆-C₇-C₈ −180.0(8) C₄₁—N₃—C₅₂-C₄₇ −1.1(8) C₅-C₆-C₇-C₈ 1.8(14) Al—N₃—C₅₂-C₄₇ 156.0(5) C₁-C₆-C₇-C₁₂ 1.0(8) C₄₈-C₄₇-C₅₂-C₅₁ 0.9(11) C₅-C₆-C₇-C₁₂ −177.1(7) C₄₆-C₄₇-C₅₂-C₅₁ −179.7(7) C₁₂-C₇-C₈-C₉ −1.5(11) C₄₈-C₄₇-C₅₂—N₃ −177.8(6) C₆-C₇-C₈-C₉ 179.6(7) C₄₆-C₄₇-C₅₂—N₃ 1.6(9) C₇-C₈-C₉-C₁₀ 0.8(11) C₇₂—N₄—C₆₁-C₆₂ 175.8(7) C₈-C₉-C₁₀-C₁₁ −0.7(11) Al—N₄—C₆₁-C₆₂ −62.9(9) C₉-C₁₀-C₁₁-C₁₂ 1.4(11) C₇₂—N₄—C₆₁-C₆₆ −2.7(7) C₁₀-C₁₁-C₁₂—N₁ −178.7(7) Al—N₄—C₆₁-C₆₆ 118.6(5) C₁₀-C₁₁-C₁₂-C₇ −2.1(10) C₆₆-C₆₁-C₆₂-C₆₃ 0.3(11) C₁—N₁—C₁₂-C₁₁ 178.1(7) N₄—C₆₁-C₆₂-C₆₃ −178.0(6) Al—N₁—C₁₂-C₁₁ 17.6(11) C₆₁-C₆₂-C₆₃-C₆₄ 1.2(11) C₁—N₁—C₁₂-C₇ 1.2(8) C₆₂-C₆₃-C₆₄-C₆₅ −1.3(12) Al—N₁—C₁₂-C₇ −159.3(5) C₆₃-C₆₄-C₆₅-C₆₆ −0.1(12) C₈-C₇-C₁₂-C₁₁ 2.2(11) C₆₂-C₆₁-C₆₆-C₆₅ −1.7(11) C₆-C₇-C₁₂-C₁₁ −178.7(6) N₄—C₆₁-C₆₆-C₆₅ 176.9(6) C₈-C₇-C₁₂—N₁ 179.4(6) C₆₂-C₆₁-C₆₆-C₆₇ −177.1(7) C₆-C₇-C₁₂—N₁ −1.4(8) N₄—C₆₁-C₆₆-C₆₇ 1.5(8) C₃₂—N₂—C₂₁-C₂₂ −177.2(7) C₆₄-C₆₅-C₆₆-C₆₁ 1.5(11) Al—N₂—C₂₁-C₂₂ 7.2(10) C₆₄-C₆₅-C₆₆-C₆₇ 175.8(8) C₃₂—N₂—C₂₁-C₂₆ 2.3(7) C₆₁-C₆₆-C₆₇-C₆₈ 177.3(8) Al—N₂—C₂₁-C₂₆ −173.4(5) C₆₅-C₆₆-C₆₇-C₆₈ 2.5(14) C₂₆-C₂₁-C₂₂-C₂₃ −2.6(10) C₆₁-C₆₆-C₆₇-C₇₂ 0.5(8) N₂—C₂₁-C₂₂-C₂₃ 176.8(6) C65-C66-C₆₇-C₇₂ −174.3(7) C₂₁-C₂₂-C₂₃-C₂₄ 2.1(10) C72-C67-C₆₈-C₆₉ 1.5(11) C₂₂-C₂₃-C₂₄-C₂₅ 0.4(11) C66-C67-C₆₈-C₆₉ −175.0(8) C₂₃-C₂₄-C₂₅-C₂₆ −2.4(11) C67-C68-C₆₉-C₇₀ −0.4(12) C₂₂-C₂₁-C₂₆-C₂₅ 0.7(11) C68-C69-C₇₀-C₇₁ 1.0(11) N₂—C₂₁-C₂₆-C₂₅ −178.8(6) C₆₉-C₇₀-C₇₁-C₇₂ −2.6(11) C₂₂-C₂₁-C₂₆-C₂₇ 178.1(6) C-₇₀-C₇₁-C₇₂-C₆₇ 3.7(11) N₂—C₂₁-C₂₆-C₂₇ −1.4(8) C₇₀-C₇₁-C₇₂—N₄ 179.5(6) C₂₄-C₂₅-C₂₆-C₂₁ 1.9(10) C₆₈-C₆₇-C₇₂-C₇₁ −3.2(11) C₂₄-C₂₅-C₂₆-C₂₇ −174.8(7) C₆₆-C₆₇-C₇₂-C₇₁ 174.2(6) C₂₁-C₂₆-C₂₇-C₂₈ 178.6(8) C₆₈-C₆₇-C₇₂—N₄ −179.6(6) C₂₅-C₂₆-C₂₇-C₂₈ −4.4(15) C₆₆-C₆₇-C₇₂—N₄ −2.3(8) C₂₁-C₂₆-C₂₇-C₃₂ −0.1(8) C₆₁—N₄—C₇₂-C₇₁ −173.1(7) C₂₅-C₂₆-C₂₇-C₃₂ 176.9(7) Al—N₄—C₇₂-C₇₁ 65.6(8) C₂₆-C₂₇-C₂₈-C₂₉ 179.0(8) C₆₁—N₄—C₇₂-C₆₇ 3.0(7) C₃₂-C₂₇-C₂₈-C₂₉ −2.4(11) Al—N₄—C₇₂-C₆₇ −118.3(5) C₂₇-C₂₈-C₂₉-C₃₀ −0.1(12) C₂₈-C₂₉-C₃₀-C₃₁ 1.2(11) ^(a)The numbers in parentheses are the estimated standard deviations in the last significant digit. ^(b)Atoms are labeled in agreement with FIG. 2A. Polymerizations

Polymerizations were performed in a glass-lined 20-milliliter autoclave reactor equipped with a mechanical stirrer, an external heater for temperature control, a septum inlet and a regulated supply of dry nitrogen and ethylene in an inert atmosphere (Nitrogen) glove box. The reactor was dried and degassed thoroughly at 115° C. The diluent and comonomer were added at room temperature and atmospheric pressure. The reactor was then brought to process pressure and charged with ethylene while stirring at 800 RPM. The activator and catalyst were added via syringe with the reactor at process conditions. The polymerization was continued while maintaining the reaction vessel within 3° C. of the target process temperature and 5 psig of target process pressure (by automatic addition of ethylene on demand) until a fixed uptake of ethylene was noted (corresponding to ca. 0.15 g polymer) or until a maximum reaction time of 20 minutes had passed. The reaction was stopped by pressurizing the reactor to 30 psig above the target process pressure with a gas mixture composed of 5 mol % Oxygen in Argon. The polymer was recovered by vacuum centrifugation of the reaction mixture. Bulk polymerization activity was calculated by dividing the yield of polymer by the total weight of the catalyst charge by the time in hours and by the absolute monomer pressure in atmospheres. The specific polymerization activity was calculated by dividing the yield of polymer by the total number of □moles of transition metal contained in the catalyst charge by the time in hours.

Example 23

Me₂Si(4-Ph,2-MeInd)₂ZrMe₂ was reacted with [NC₁₂H₈]₄Al(H) in a ratio of 1:3 and left at room temperature for one day. Table 19 depicts the ethylene-octene copolymerization data.

Example 24

Me₂Si(Ind)₂Zr(CH₃)₂ was reacted with [NC₁₂H₈]₄Al(H) in a ratio of 1:3 and left at room temperature for one day. Table 19 depicts the ethylene-octene copolymerization data.

Example 25

(1,3-MeBuCp)₂Zr-Me₂ was reacted with [NC₁₂H₈]₄Al(H) in a ratio of 1:3 and left at room temperature for one day. Table 19 depicts the ethylene-octene copolymerization data.

TABLE 19 EO Polymerizations via Me₂Si(4-Ph,2-MeInd)₂ZrMe₂, Me₂Si(Ind)₂Zr(CH₃)₂ & (1,3-MeBuCp)₂Zr—Me₂/[NC₁₂H₈]₄Al(H). Actual Activity Comonomer Average Average Average Quench Catalyst (g · Pol./μmol. Catalyst Incorporation Mw Mn PDI Time Yield Micromoles Cat · hr) EX23: Me₂Si(4- 2400.6 0 0.0125 0 Ph,2- 2400.15 0.004 0.0286 0.209 MeInd)₂ZrMe₂ 21.7 431054 276319 1.56 851.4 0.059 0.0446 5.58 21.7 403912 256802 1.57 365.84 0.082 0.0607 13.37 23.2 382385 244384 1.56 327.84 0.089 0.0768 12.8 24.2 355829 222995 1.60 278.66 0.096 0.0929 13.4 24.1 330292 209431 1.58 257 0.103 0.1089 13.2 23.8 330891 210577 1.57 223.4 0.099 0.125 12.8 EX 24: 2400.89 0 0.0125 0 Me₂Si(Ind)₂Zr— 2401.1 0.0023 0.0286 0.120 (CH₃)₂ 2400.99 0.013 0.0446 0.456 8.65 107014 73534 1.46 2401.17 0.040 0.0607 1.00 9.03 107128 73413 1.46 1560.1 0.043 0.0768 1.29 8.58 104397 71743 1.46 1205.22 0.046 0.0929 1.50 9.08 100773 68211 1.48 945.07 0.046 0.1089 1.62 7.43 100686 68432 1.47 942.13 0.050 0.125 1.55 EX 25: (1,3- 2400.3 0 0.0125 0 MeBuCp)₂Zr— 2400.46 0.010 0.0286 0.545 Me₂ 2.96 194149 132623 1.46 211.42 0.035 0.0446 13.4 2.54 197887 134989 1.47 235.44 0.055 0.0607 14.0 3.13 153515 104255 1.47 155.61 0.063 0.0768 19.0 2.68 138614 93225 1.49 144.78 0.068 0.0929 18.2 3.31 132623 88875 1.49 109.44 0.075 0.1089 22.8 3.05 125087 83298 1.50 105.12 0.076 0.125 20.9

Unless otherwise indicated, all numbers expressing quantities of ingredients, properties, reaction conditions, and so forth, used in the specification and claims are to be understood as approximations based on the desired properties sought to be obtained by the present invention, and the error of meausurement, etc., and should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and values setting forth the broad scope of the invention are approximations, the numerical values set forth are reported as precisely as possible.

All priority documents are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted. Further, all documents cited herein, including testing procedures, are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted.

While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. 

1. A catalyst system comprising: a polymerization catalyst; and an activator comprising two or more heterocyclic nitrogen-containing ligands coordinated to a Group 13 atom, wherein the activator is a reaction product of one or more Group 13 atom-containing compounds and one or more heterocyclic nitrogen-containing compounds.
 2. The catalyst system of claim 1, wherein the compounds are reacted at conditions sufficient for at least one proton located at a first position on at least one of the heterocyclic nitrogen-containing compounds to migrate to a second position upon nitrogen coordination to the Group 13 atom.
 3. The catalyst system of claim 1, wherein the two or more heterocyclic nitrogen-containing ligands comprises at least one indolyl and at least one indolium.
 4. The catalyst system of claim 1, wherein the two or more heterocyclic nitrogen-containing ligands comprises at least one carbazole and at least one carbazolyl.
 5. The catalyst system of claim 1, further comprising a support material treated with aluminoxane or an alkyl aluminum compound such that the support comprises aluminum alkyls groups bonded thereto.
 6. The catalyst system of claim 1, wherein the one or more heterocyclic nitrogen-containing compounds is selected from the group consisting of pyrroles, imidazoles, pyrazoles, pyrrolines, pyrrolidines, purines, carbazoles, indoles, phenyl indoles, 2,5, dimethyl pyrroles, 3-pentafluorophenyl pyrrole, 3,4 difluoropyrroles, and combinations thereof.
 7. The catalyst system of claim 1, wherein the one or more heterocyclic nitrogen-containing compounds comprises at least one indole selected from the group consisting of 4-bromoindole, 4-chloroindole, 4-fluoroindole, 5-bromoindole, 5-chloroindole, 5-fluoroindole, 4,5,6,7-tetrafluoroindole, 2-methylindole, and 3-methylindole.
 8. The catalyst system of claim 1, wherein the heterocyclic compound is substituted with one or more substituent groups selected from the group consisting of a halogen atom and a halogen atom-containing group.
 9. The catalyst system of claim 1, wherein the heterocyclic compound is substituted with one or more substituent groups selected from the group consisting of chlorine, bromine, iodine, and fluorine.
 10. The catalyst system of claim 1, wherein the polymerization catalyst comprises one or more metallocenes.
 11. The catalyst system of claim 1, wherein the Group 13 atom comprises aluminum or boron.
 12. A catalyst system, comprising: a polymerization catalyst; and at least one activator represented by any one of the following formulas: (R′_(x)M(JY)_(y))_(n) or  (a) [((JY)_(y)R′_(x))_(n)M-O-M((R′_(x)(JY)_(y))_(n)]_(m) or  (b) (OMR′_(x)(JY)_(y))_(n)  (c) wherein: M is a Group 13 atom; O is oxygen; (JY) is a heterocyclic nitrogen-containing ligand coordinated to M; R′ is a substituent group bonded to M; x is an integer from 0 to 4; y is 2 or more; x+y=the valence of M in formula (a); x+y=the valence of M−1 in formula (b); and x+y=valence of M−2 in formula (c); n is 1 or 2 in formula (a); n is 2 in formula (b); and n is an number from 1 to 1,000 in formula (c); and m is a number from 1 to
 10. 13. The catalyst system of claim 12, wherein the activator is a reaction product of one or more Group 13 atom-containing compounds and one or more heterocyclic nitrogen-containing compounds.
 14. The catalyst system of claim 12, wherein the activator is a reaction product of one or more Group 13 atom-containing compounds and one or more heterocyclic nitrogen-containing compounds, and the compounds are reacted at conditions sufficient for at least one proton located at a first position on at least one of the heterocyclic nitrogen-containing compounds to migrate to a second position upon nitrogen coordination to the Group 13 atom.
 15. The catalyst system of claim 12, wherein (JY)_(y) comprises at least one indolyl and at least one indolium.
 16. The catalyst system of claim 12, wherein (JY)_(y) comprises at least one carbazole and at least one carbazolyl.
 17. The catalyst system of claim 12, further comprising a support material treated with aluminoxane or an alkyl aluminum compound such that the support comprises aluminum alkyls groups bonded thereto.
 18. The catalyst system of claim 12, wherein the heterocyclic nitrogen-containing compounds is selected from the group consisting of pyrroles, imidazoles, pyrazoles, pyrrolines, pyrrolidines, purines, carbazoles, indoles, phenyl indoles, 2,5, dimethyl pyrroles, 3-pentafluorophenyl pyrrole, 3,4 difluoropyrroles, and combinations thereof.
 19. The catalyst system of claim 12, wherein the one or more heterocyclic nitrogen-containing compounds includes at least one indole selected from the group consisting of 4-bromoindole, 4-chloroindole, 4-fluoroindole, 5-bromoindole, 5-chloroindole, 5-fluoroindole, 4,5,6,7-tetrafluoroindole, 2-methylindole, and 3-methylindole.
 20. The catalyst system of claim 12, wherein the heterocyclic compound is substituted with one or more substituent groups selected from the group consisting of a halogen atom and a halogen atom containing group.
 21. The catalyst system of claim 12, wherein the heterocyclic compound is substituted with one or more substituent groups selected from the group consisting of chlorine, bromine, iodine, and fluorine.
 22. The catalyst system of claim 12, wherein the polymerization catalyst comprises one or more metallocenes.
 23. The catalyst system of claim 12, wherein the Group 13 atom comprises aluminum or boron.
 24. The catalyst system of claim 12, wherein the polymerization catalyst comprises one or more metallocenes, Group 15-containing compounds, phenoxide transition metal compositions, Group 5 or 6 metal imido complexes, bridged bis(arylamido) Group 4 compounds, derivates thereof, or combinations thereof.
 25. The catalyst system of claim 12, wherein each R′ is independently selected from the group consisting of hydrogen, linear or branched alkyl radicals, linear or branched alkenyl radicals, linear or branched alkynyl radicals, cycloalkyl radicals, aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl radicals, dialyl radicals, carbamoyl radicals, acyloxy radicals, acylamino radicals, aroytamino radicals, straight alklene radicals, branched alklene radicals, cyclic alkylene radicals, derivatives thereof, and combinations thereof.
 26. The catalyst system of claim 12, wherein each R′ is bonded to the support material and is independently selected from the group consisting of hydrogen, linear or branched alkyl radicals, linear or branched alkenyl radicals, linear or branched alkynyl radicals, cycloalkyl radicals, aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals alkylthio radicals, dialkylamino radicals, alkoxycarbonyl radical, aryloxycarbonyl radicals, carbomoyl radicals, alkyl radicals, dialkyl radicals, carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight alkylene radicals, branched alkylene radicals, cyclic alkylene radicals, derivatives thereof, and combinations thereof.
 27. An aluminum activator comprising two or more heterocyclic nitrogen-containing ligands coordinated to an aluminum atom.
 28. The compound of claim 27, wherein the coordination of the heterocyclic nitrogen containing ligands to the aluminum atom causes a proton on at least one of the ligands to migrate from a first position thereof to a second position thereof.
 29. The compound of claim 27, wherein the activator is a reaction product of one or more Group 13 atom-containing compounds and one or more heterocyclic nitrogen-containing compounds selected from the group consisting of pyrroles, imidazoles, pyrazoles, pyrrolines, pyrrolidines, purines, carbazoles, indoles, phenyl indoles, 2,5, dimethyl pyrroles, 3-pentafluorophenyl pyrrole, 3,4 difluoropyrroles, derivatives thereof, radicals thereof, and combinations thereof.
 30. The compound of claim 27, wherein the two or more heterocyclic nitrogen-containing ligands comprise at least one indolyl and at least one indolium coordinated to the aluminum atom.
 31. The compound of claim 27, wherein the two or more heterocyclic nitrogen-containing ligands comprise at least one carbazole and at least one carbazolyl coordinated to the aluminum atom.
 32. A catalyst system comprising: a polymerization catalyst; and an activator comprising two or more heterocyclic nitrogen-containing ligands coordinated to a Group 13 atom, wherein the activator is a reaction product of one or more Group 13 atom-containing compounds and one or more heterocyclic nitrogen-containing compounds; wherein the compounds are reacted at conditions sufficient for at least one proton located at a first position on at least one of the heterocyclic nitrogen-containing compounds to migrate to a second position upon nitrogen coordination to the Group 13 atom.
 33. A catalyst system, comprising: a polymerization catalyst; and at least one activator represented by any one of the following formulas: (R′_(x)M(JY)_(y))_(n) or  (a) [((JY)_(y)R′_(x))_(n)M-O-M((R′_(x)(JY)_(y))_(n)]_(m) or  (b) (OMR′_(x)(JY)_(y))_(n)  (c) wherein: M is a Group 13 atom; O is oxygen; (JY) is a heterocyclic nitrogen-containing ligand coordinated to M; R′ is a substituent group bonded to M; x is an integer from 0 to 4; y is 2 or more; x+y=the valence of M in formula (a); x+y=the valence of M−1 in formula (b); and x+y=valence of M−2 in formula (c); n is 1 or 2 in formula (a); n is 2 in formula (b); and n is an number from 1 to 1,000 in formula (c); and m is a number from 1 to 10; wherein the activator is a reaction product of one or more Group 13 atom-containing compounds and one or more heterocyclic nitrogen-containing compounds, and the compounds are reacted at conditions sufficient for at least one proton located at a first position on at least one of the heterocyclic nitrogen-containing compounds to migrate to a second position upon nitrogen coordination to the Group 13 atom. 